Well, reserve officials are set to meet about raising interest rates again starting tomorrow and most expect them to increase rates by another three-quarters of a percentage point for the third time since June and signal plans for another smaller increase in December. This as inflation has proved more stubborn than the feds say expected, with markets reacting especially poorly in the last month. Joining us live now to discuss this more is CEO of Stock Swoosh, Melissa Armo. Good to see you, Melissa. Thanks for having me. So how do you think the markets will react to this latest news? I know a lot of them have been expecting it, but what do you think they'll do? Well, I think the big thing for the next two days when the Fed meets is not necessarily are they going to raise interest rates. Hello. I can hear you, Melissa. Can you hear me? Yeah, someone else was talking to me. No worries. No, no, no, no. You're fine. Go ahead. As I was saying, I think the big thing for the last this next two days is not whether or not the Fed is going to increase rates. They are going to 75 basis points, but it's going to be what they're going to say what's going to happen going forward. So a lot of people, like you just said, think that they're going to not raise rates as much going forward or into 2023. But I think the problem is that what if they don't do that? They've given no indication that they're going to stop raising rates. We still don't have inflation under control. And the Fed seems to think that continually raising rates is going to solve the problem. Personally, I think the problem is the cost of fuel, diesel fuel, gasoline. I think these things are problems.  Diesel prices have gone up. And so everything we buy costs more because of that. And raising rates really isn't going to change the cost of fuel. Which is interesting because, again, they thought it was going to be transitory inflation. These are the same people that didn't predict this happening.  And as you mentioned, they continue to raise rates, thinking that you keep doing the same thing, that you're going to get a different result. But you mentioned diesel fuel. That's impacting a lot of states around here. How much of an impact do you think that is going to have on the economy if they don't take control of the situation here soon? Well, they're not going to take control of the situation. They haven't. They're not. The energy policies of this administration, unfortunately, have not been kind to the oil industry. So one thing I'd say to people if they're looking and if they really want to invest in something right now, they can invest in oil. Because the prices of oil stocks have just been skyrocketing. Whereas the prices for stock, the overall market, have been trending down for 2022. But you've had an increase in prices rising for a lot of oil stock. So I don't see anything changing right now as long as the administration is in place. And obviously, we're going into the midterms. But the problem is that the next presidential election is two years out. Right. So a lot can happen in the coming weeks and months ahead. Again, midterms coming up Tuesday.  But they're still spending a lot more on everything, double sometimes, in some cases, triple. How do they weather through the storm? What advice do you have for them? Well, I think people just have to weather in the storm, whatever that means. I mean, if it means getting a second-per-time job right now, if it means not contributing as much to the 401k, so they have more take-home pay.  These are regular things like gas, food, housing, fuel costs. I mean, everybody needs to pay for these things in order to survive and live. So while you might want to spend less on maybe entertainment or going to vacations in the next 12 months, I really think this is not going to last forever. Again, luckily, we have a presidential election coming up in two years. But it could last a while. It could last for another 12 to 24 months. So people need to be aware of that. I know they said about two years ago that they thought inflation was temporary. They were wrong about that. And so people need to plan ahead accordingly, going into 2023. And take advantage of some things. Like you said, maybe invest in oil if they can. Well, I mean, oil stocks have been rising. So they've been making new highs. The market is nowhere near the highs. And, you know, we're going to close out the year wherever we close out. But it's not going to be near the highs. Any other advice, because, you know, the pendulum always swings and there are some economists out there saying that there are some deals to be had. So for real Americans that want to look at the silver lining there, what should they be taking advantage of right now? Well, right now, nothing. But the deals to be had means keep a keep a positive optimistic attitude. Because even if your 401k has gone down, which everyone's had since the beginning of the year, there will be time to invest again. Personally, I don't think it is right now between now and the end of 2022. I would wait to see what happens with the rushing and praying conflict and wait to see what happens with the midterms and going into the beginning of 2023. But there'll be a time to invest again. And then the market will rise. The market's not going to stay in the same trend it's been for the last 10 months forever. So we'll get a lift and then people will recover from their retirement savings. And again, everyone has a different age point as far as how long they have to invest to wait to ride it up. But the one thing about the market is it can fall fast and it can rise fast. I'd say sit tight right now, but stay optimistic about the future.  Lee Zeldin now leading Kathy Huckle there for one percentage point, according to recent polls right there, something that we haven't seen happen in New York forever and large part due to the economy. And because of these vaccine mandates, not to mention the migrants that have been shipped to your state. How hopeful are you that Lee Zeldin could win it? I'm really, I'm so hopeful.  And again, Schumer is running against, you know, Pinion and he actually did really good. Joseph Pinion did really good last night in the debate against Schumer. So, I mean, New York could change.  Remember, Kathy Huckle did not run for governor and win. So, she's not an elected governor of New York. She was appointed after Pomo was put out. So, I mean, I watched the debate. It wasn't on TV, unfortunately, locally. I don't know why, but I didn't watch it live in an app. And she had really no response to anything except for Trump. It was Trump this, Trump this, Trump that, but Trump, Trump, Trump, Trump. It was the worst debate I ever saw. All she wanted to do is talk about Trump. These people live in the past. Lee Zeldin has nothing to do with Trump and fixing New York state. And all they want to do is talk about Trump. And if Trump decides to run again in 2024, unfortunately, I think the country is going to be even more divided than it is right now. And then it wasn't 2020 without election. Everybody said, well, Biden is going to come in and Biden is going to bring everyone together. That's what everybody said. And that's what he said, too. But that's not the case. Things have gotten worse economically and people are even more divided. Yeah. And as you said, it's pushed Democrats in that state to now want to vote for Lee Zeldin. So, we'll continue to have the latest results on that again on Real America's Voice next Tuesday. It is going to be interesting to say the least. I'm Melissa Harmo with Stock Swoosh. As always, thank you so much for joining us here on Real America's Voice. Thanks. Coming up after the break.


The following is a presentation of TFNN, the Tiger Technician Hour with your host, Basil Chapman. Call now. Call free at 1-877-927-6648. I want to talk. Yeah. We think we can get going on this first week, Tuesday, the 6th of September with the SB down 28, 38, 95. There was a discussion. There was a discussion in the Tiger Den about the Roman candle. What's the Roman candle? Well, that's part of my Chapman Wave methodology. A Roman candle is where the price usually at highs, you see that. And what happens is the price of whatever you're following opens higher, makes it tighter. The wick has a huge candle to the downside that closes that particular bar, either half or two thirds off the base low of that wick. And this case, at the high, all-time high, 48, 18.62, the S&P made a high, and then it opened at 47, 78, 18, popped to 48, 18.62, ran down to 42, 22.62, which was the 14-period exponential moving average, which it hadn't even touched since back in June or so of 2020. So that was significant, but then closed at 45, 15.55. And that produced a candle that I said, uh-oh, the rule of the Chapman Wave methodology is if at a high you get this red candle, and the reason why I called it a Roman candle is it makes this tiny little wick. And you know with a Roman candle, you light the wick and it blows up. And my rule of thumb is within two bars, if there is a short-term close, and in this case I said on a daily basis, halfway into the wick, and that would have been around about 42.22, halfway into the lower part of the wick, be careful because that suggests there's going to be a very quick move down to the lower, maybe even close at the low. Well, we did that once. We did that the following session. That was the first one was January 2022. The second one was February. And that took two bars in which to break down. And then we went lower and lower until 36, 36, 2087 was the low that was formed back in June of this year. So that's the essence of it. And why is it important if you remember those of you who are around when we made that high back in, right there, back in October of 2007, there was a kind of almost a doji candle at the high of October in the following month, September. I said, uh-oh, I had to wait for the September candle to close. And I said, uh-oh, a type of Roman candle at a high. And that imparts the information that says, well, watch out because if you start closing below that low, look, we did three months later. We did that huge Roman candle and closed below it. So yes, it's a very important technical indicator. And that's the reason why I've been saying that, yes, we have made some kind of a top in the shorter term. Then I went to the intermediate term in the dating chart for intermediate term cell signal. Then the weekly went from a cell signal to a cell mode. And then I said until we close on a monthly basis below the nine closes below the 14 period in the monthly chart. Yes, we could possibly have a buy signal, but it's very unusual at a P, B, not to go to a C and a D, but all the other indices that already made D, E, F, and that said, got to be really careful. So in this particular instance, September is going to be a very, very important month, why? Because so far, you've got an S. And that's the first time you've got that in the monthly chart in a very long time. You've got an S in the monthly chart of the Dow, but we're only a couple of sessions into September. We have to wait for the whole month of September to see if that's concluded as a negative. And then we're going from a cell, we're going to have a cell signal. I don't know yet if we're calling it a cell mode, but certainly a cell signal. So everything is in play here, and that's the reason why I raised stops that we've got a pretty, very high, in fact, cash position at this point. Yes, we are trying to buy the Dow for at least a counter and rally. And yes, on Friday I had mentioned that we had bought, actually no, I didn't mention it. Subscribers know about this, that we bought just before the close, we bought a little extra insurance for our short the Dow via the INDU, via the DOG. And that says, and that was from the 22nd, I think it was, of last month. Let me just get to this. So what we're doing right now is we're looking at, oh, I didn't type that in. Yes, it should have been in there. Oh, it's in this chart right here. That shows you there, short right there. And we wanted to add to it, I took that off this morning, actually I probably should have held it because I treated it only as insurance because all of the negativity at the end of last week said that over the week, long weekend, there could be just a horrible move on Sunday night into Monday in the futures market and that would carry through to Monday, but that was the exact opposite. But now we do have that. So as it says right now, overall, the only position we have now is the short side of the Dow. And we're waiting to see how this unfolds. And the more I thought about it, the more I did the work over the weekend, I came to two conclusions. One is that the market is now a trading vehicle. And that's how you have to consider it. Trading on the short side, the long side, very quick moves. I don't know if you want to use two or three times positions. I'd say that's kind of, that's just a little high risk. In this case just for me at this particular moment, but in fact, if you're looking at the SMHs, the semiconductors, look, they're making new lows as we speak. And that's not a good sign, especially after the weekly chart. Didn't have such a fantastic move to the upside when you think 318.69 double top in January from the November high. And then it pulls back very sharply from 318 to the 204 area. That, it's not a very bad move chart wise because you were coming off a low, just certainly the low from March of 2020 and 96 round number low to 318 spectacular move to the upside. But this is starting to get a little more serious in this weekly chart because, excuse me, the low that was made just recently in the 200, no, this is the one that was at 188 or something like that, let me see what it was. 189.94, it's just becoming closer and closer. If we move underneath that, that's not going to be a good sign at all. So yeah, I'm suggesting cash is a position. It's not a cop-out, it is a position. And we are now in a very heavy cash position. And number one, number two is within the context of balances. This balance, if you look at SMH's little bounce for the last two sessions, that's not very good. If you're looking at the Dow, looking at the balance, where did that go? Dow, there it is. Yeah, it's the same thing. We failed in the rally on Friday and we went to a lower low and now we've made a lower low stop. So that just says that now you can have rallies but you've got to look at this. It's a 950 L average of $35,895. $2,188. If you think average, that's going to be strong resistance. It's a good bet. I'll be back in a minute. Vista Gold owns and operates the largest undeveloped gold project in Australia, the Mount Todd Gold Project. Vista Gold just completed their feasibility study, resulting in a 7 million ounce gold reserve. Vista Gold has all major permits approved and has retained CIBC capital market assistance in evaluating alternatives and in completing an accretive transaction. Vista Gold trades on the NYSE American and TSX under the ticker symbol VGZ. Vista Gold executing strategy to create shareholder value. Are you looking for a way to consistently add winning trades to your portfolio? Tom O'Brien is here to help. 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Larry will also provide daily charts, videos, and data on the key markets that he's tracking. Expect notifications from Larry on market movement you need to act on at any time. First-time subscribers also get a 30-day money-back guarantee. If you're not satisfied, let us know and you'll get a full refund within 30 days of signing up. Subscribe to the Fibonacci 24-7 newsletter today TFNN.com, Educating Investors. All Tigers and Tigresses for just $1 for the year. There's no catch or added costs when you join our community of traders. Sign up today and become a part of this educational community of traders. Just visit the front page of TFNN.com. The more work I did over the weekend, the more, as I concluded my subscriber video on, was a Monday morning, I, as I went through different charts over the rest of the day, going to Monday night, and I have to tell you, I did drive on Saturday and Sunday, I drove by, the US opened, I didn't actually go in. A lot of traffic there. I wish I had, but this is on my way to Brooklyn. And the tennis is absolutely fabulous and the level of playing, for me, the dexterity and the movements, it's not so much the back and forth, it's sideways, it's running to the net. I love that kind of tennis, very, very physical, very active, great tennis that we've been watching. TV, that is not the real thing. And so, the more I came to the conclusion that that's very much like the market right now. It's just really choppy, so far we have to think of more like lower highs and lower lows. That's the shorter term. The other aspect that I, that, based on the candle that I spoke about in the S&P, the monthly candle at the high, the championship Roman candle, where if you trade within a very short timeframe, halfway into the wick, the lower long wick, there's a real good chance you're going to take out the low and then go even lower. That sets in place an activity within markets that I think we cannot rule out. And that is regardless of how we chop and how high we go in this interim period, until we make a really strong V-shape low and it doesn't have to be a V-shape low that has to be retested. I like to talk about an internal low and a residual low or the earthquake and the aftershock. But that V-shape, I think going to a lower low and then rebounding very sharply and as we go into the lower low, if you look back just three bars to the actual lower low point of the ictus, the turnaround moment, you usually find that it's 15, sometimes even 20%, just the last move down gives you this extra negative activity before it turns around. Then you look back and say, wow, look at that. Within days we were above what we were just whatever number of days ago. And that says to me that you need a lot of patience and there's nothing wrong in having cash handy. I just think it's really important to be building up some kind of what we can call a kitty or at least some way that you can start entries on that V-shape low if we're able to identify it whereby you can start initially having a wide stop and then make that stop tighter and tighter until there's a gain and then you can say, okay, I know exactly what I'm prepared to lose. I don't know what I can gain but I know what I'm prepared to lose. So in that aspect, I don't think we're there. I think the news reports are coming out and we're going to find that the weakening even in the housing sector, but especially so in the jobs sector, there's going to be a mental change. You know, in housing when you want to sell place and you think, oh man, it's going for, let's just make up a number, let's just say 400,000 and it's going for 400,000. I'm not prepared to accept anything less than 420 and all of a sudden somebody comes in and says, I'll give you 400 cash.  The person who was offering 380 comes in and says, okay, well, 360, take it or leave it and that's kind of what we're looking at the job market that people were saying, oh yeah, I'm working at home. I love working at home. I'm not going back to the office and all of a sudden that whole aspect of your income shrinking, the job disappearing or at least being threatened and then your children say, okay, I'll accept it. By that time the company is already starting to shrink their employment activity. They say, okay, well, you know, at this particular time where the markets are soft maybe we don't need to increase our employment numbers. So this is, I think that's what we're looking at and therefore I think there's more time that's needed here before we can actually get a low of significance, one that really has the potential to move the markets 30 to 35% up. So that's where I stand right now and also with the patterns that we're looking at with that weekly pattern fading again going underneath the chapwave inside track, I just don't feel that I need to be aggressive here. In fact, this is one of those cases where we will have enough money to deploy if we start to see higher highs and higher lows. Just keeping it as simple as possible. All right. Now, within that context, a couple of questions that came in over the weekend. Let me see if I can get to them now. Yeah. Can you look at Amazon? Is this time to increase your, you said nibble on Amazon? What do you feel like now? I'm still in the nibble camp. There was that one moment it was at, I think it was in the area of 134, 135 and now it's at 125 and I'm still not, that was just like a pilot light just getting a little foot in the door, a little pinky in the door to say, hey, how are you acting while the markets in this particular phase? I don't want to be in Amazon on a big, at this point to increase anything other than just that little pilot light nibble. Let's see what happens. I want to see by the end of the week, has Amazon held 122? I think it was. See the gap high the day before the actual gap up, the high that day was 121.90 on this 27th of July, the very next session, sorry, did I do that wrong? I guess I must have moved. 122.84 was the high on the 28th and on the 29th the low was 132.41. So until I know that that, certainly the left side high that was made on the 22nd, which is 125.50, that's been tackled over the last couple of days. Not good enough. I want to see, do we get down to that level? Do we get inside into the 120 area 118 in this particular down phase? Or we now just about to start a move that says, yes, we could have another bounce before we have a real test of Amazon's strength. So I'm just saying step aside. Next question was Exxon. A lot of people have Exxon for a long time. And I've got Exxon and a peak C, even though everything about it looks like that should have been a D, but it is underneath the weekly peak F at 105.31 then 105.57 was the high of the week of the 10th of June. Just type that in. 95.5761022. And we're at 9510 right now. I think that if you're holding Exxon, having taken a little bit off when I was talking about all those other multinational oils back there and they didn't pop up that was going to choose high, I think that because I would be adding to Exxon right now. I just hold tight and see what happens, but I think we are getting close to a test in Crudel or I haven't even gotten to that. I'll be back to talk about Crudel. To see for yourself the types of profitable trades that are recommended within the Gold Report, sign up now by visiting TFNN.com. Don't miss out on the next great Gold trade. Sign up today. TFNN is excited about our new software charting program, the Art of Timing the Trade Chart. 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So, in the context of the e-mini, we've got a little bit of a turnaround here. Down 18, this looks a little too aggressive to me, so I'm going to move it over a little bit because that's what we have to do if the plum line has moved to the right and that just says, find another right here. So you'll have to find that'll be the fulcrum right there, the plum line, the moving plum line and we'll go to the right. And so, okay, if this all works out, then by what time would that be? That would be 1037. Wow, that's a little aggressive at seven minutes. 1037. Yeah, by 1037, the plum line right there should be taken out. And that is at 3915. And if that's taken out, you can see a test of the high. That looks very aggressive to me. Of the 10 o'clock high, 3920 on the September e-mini. Well, we'll come back to that. That's not so important right now. What is important is, a couple of questions came in. So, holding puts on some of the semiconductors, for instance, Intel is one. And I always think that it's always very difficult for me to do, but the rule of thumb is what you should stick with. And the rule of thumb says, if you're going to short something, short the weakest because they're the ones that show that they haven't got any strength on the upside. So, therefore, they should continue working to the downside. And remember, another rule of thumb is, stocks that make all-time highs tend to stay in that all-time high sector for a while until things change dramatically. And stocks that make all-time lows tend to do that. And Intel is one of those. So whoever said puts on Intel, at this particular point, you're right, because it's down 76 cents at 30.46 down 2.4% today. Nvidia is in the same category. Remember, the semiconductors have been acting very weird, not gone back into the semiconductors since we've had that really aggressive move to the upside. And now we're just stepping aside. And that's another reason why I don't think there's any reason to be aggressively long, but you can be specifically long. That is, either a short-term trade or a stock that's held very well against all the downside pressure. Now, this is very interesting. That was GSAS-C. And this is now coming to D in the weekly chart in Nvidia down 2.38 and 1.34. These are not... Two things. One is, if the semiconductors are failing, it says there's a good chance that the general market is going to have a tough time holding gains. And number two is when eventually the semiconductor index starts to move to the upside, that should encompass the QQQ, the index 100, and the QQQs right now are trading down. If I can just type it in right there, there it is. Yeah. Q's are down in leg E at 2.92, taking out the left-side low. So let me just draw this in. Someone said, could you just do this live on early next week? So what I do is I like to find a plum line. What is the plum line? That's the line on the way up where the market stores or the price of the tradeable, you're looking at stores on the way down, and it looks like when it turns around, you can make an equal number of bars on the right side to what it did on the left side. It's bar symmetry. I swear I had a webinar based on bar symmetry just recently, a month ago. And look at this. In the bar symmetry, you've got on the QQQ, the low that was made back in July, I'm going to say for the moment, I'm just going to say the 22nd, 23rd. If you go to the right side, you've gone down below that match in price in a quicker timeframe. One bar early. We've taken out the low that was the low of the 26th of July at 293.54, going to the peak G doji candle with the sign in doji following at 334.42 on the 16th of August. And that just says if you fail, that means that the acceleration down is greater than it was on the way up. And now you're going to look for the next support level. Well, unfortunately, that doesn't come in as a very direct trough until you go back to the 14th of July at 279.80. That's 10 points down from here. And this is a really leg E with the potential that it could be a chamois instant restart on the way down. So I don't want to mess around with this. I'm just saying that the semiconductors are not acting very well right now. We just saw that in some of the leads, like in not Intel as a lead, but Nvidia that was a favorite.  MRVL. And Marvell, it didn't even get to a D and it didn't even get to the 200 p.m. Rubing average is down 70 fees since the 4502 and a very big arch formation in the daily chart and a peak D in the monthly chart. So even some of your better ones, even applied materials, AMAT made a peak E with a doji candle and it's coming down. Oh, well the next low that we'd have to look at would be the low of the 14th of July of 86.41 and the way I do these is if it's very obvious that there's a trough that I can use. Let's get it from this one to right there. That's a very, that double top, it's just great if you can use the VOU shape bottom as a left side, right side price time match but if I do that it says, oops, got it. It says that we've already run out of time. Did I get that career? Yes, I did. So that's green and that's pink and yeah and that says it hasn't it's taking a little bit longer to get down there and this particular pattern says if it's taking a little longer there's a chance it could make that low later but then come back very quickly to test that support level so the level we're watching here is going to be 86.41 and it says 89.72 so what would I then do? I draw in the channel wave inside wedge target repellent line it would have to go to that level well that level's already we passed that level in the number of bars from the left to the right so that means I have to find another point of reference and that says I could in fact move it to the right and we take it to about the 9th of September the 9th of September is Friday and Friday it says if there's a chance by Friday we should be testing 86.41 Alright so a couple of those things I wanted to go through another question was could you show us your triple yield chart well yes I can show you that I didn't really want to add that today but I'll do that I did it for subscribers yesterday there's a triple yield chart and that's just saying the huge cup weekly cup formation that made a handle is probably going to take out the left side high and then come back into the handle because that's what cup and handle patterns do let me show you white is the 30 year brown is the 10 year yield and light blue is the 5 year yield and it should be there right now it should be there right now alright if it's not there right now it should be there right now and there it is so here we go you see the white is just sneaking above the cyan that's the 30 year that's a good sign actually it says maybe the inversion is just kind of not as bad as it was so you can see it 3457 for the yield 3.457 is just a 10 under 3.472 by that was right back in 7.844 by 24th of June I'll be back in a moment oh is that true yeah you got speed down I'll be back in a moment you might think that if you want to be successful at trading in the stock market you're going to need a crystal ball after all it's impossible to predict the future right like any endeavor in life before you decide it's impossible get some advice from the experts you might find that it's not so impossible after all for daily market overviews that give you direction on the key indices selective stocks and commodities subscribe to the opening 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well as entry prices and stops to set for each trade Dave delivers his weekly newsletters every Friday with updates throughout the week you can get the technology insider at tfnn.com for only $37.50 sign up for David's newsletter the technology insider and get an inside look at everything the technology sector has to offer try it risk free today with our 30 day money back guarantee tfnn educating investors biotech is booming but for how long whether you think the biotech bull has room to run or has run its course trade LABU or LABD directions daily S&P biotech 3 times bull and bear ETFs visit directioninvestments.com slash biotech today an investor should consider the investment objectives risks charges and expenses of the direction chairs carefully before investing the prospectus and summary prospectus contain this and other information about direction shares to obtain a prospectus or summary prospectus please contact direction shares at<PHONE_NUMBER> the prospectus or summary prospectus should be read carefully before investing an investment in the funds is subject to risk including the possible loss of principal the funds are designed to be utilized only by sophisticated investors such as traders and active investors distributor foresight fund services LLC this program is brought to you by vista gold traded on the NYSE American and TSX under the symbol VGZ so because of the discussion about the chapter of roman candle I completely forgot about just going through all the different indices as I always do so let me just do that now and also it's a little late and maybe it's a couple of minutes late but we did get to that exact level in the S&P E-mini that I was targeting the 39 whatever it was over there 39.18 39 25.50 level we made 30 right there we made 39.25 50 at 1041 all right that's the technique and the closer we get to 323 on the next rally if it is then the 39.27 200 period moving average becomes a target okay let's get back to our story here so this is what I wanted to talk about in the gold so the gold right now is down four and a half at 17.18 one of the aspects that I've been very impressed with was that the the fact that the dollar is streaming at all time yearly highs or in multi-year highs let's just say remember because we still got that whole area in the highs that were made way back in the dollar so that's at least recovery highs but what we're looking at is that gold is holding pretty darn well when you think about it individual gold stocks some of them have got pummeled some of them are holding okay but more importantly what I am looking at is the gold the patent that we're looking at has got this huge cup formation this is the opposite of we were looking at in the weekly chart of the bonds where I say a cup and handle not one of my favorite patterns at all unless you get the low of the cup handle and then you can write it so that it bounces high and then comes back to retest the lip of the cup well this is the exact opposite in the gold it's also got the Chapman folding ax formation the inverted folding ax formation rising lows and much higher highs then it turns around but if it makes a peak C, D or E and then comes back in this particular expanding cone formation usually all that happens is a retest for low it can even slip a little bit lower but it doesn't break down like the dreaded H pattern when it fails at a peak B or an A so this is a leg A this is a little miniature dreaded H now that's different so if this A starts to plummet the 1680 area is really important to hold on a continuous contract for gold meantime back at the ranch this is it's doing okay the MACD is improving histogram wise but it's not great the stochastic is okay 26 but it's really not good on balance volumes down the 9th period is way under the 14th gold there's a lot to do but the fact that it's holding okay is very impressive the fact that silver is making low lows and low highs in the weekly chart but the daily chart is that a little bit of a pop-up is okay but it just says to me that if silver plays catch up to gold to actually lead it's going to have to do a lot more it's 18 right now 18.02 huh it needs to get to the 2150 area sometime in September to say hey I'm back in the running at this point it's just not in the running it's just running and if you're looking at high grade copper high grade copper is down at the lower end but it's holding okay not great I always put it together with wood the ice is global timber and forestry ETF which is not that great now it's actually very weak we were doing well before now it's not doing well at all so that just tells me internationally there's a whole spectrum that goes together with high grade copper which is an international benchmark for building activity together with the ice is timber and forestry ETF and that just says who this is not a great time if you look at the HGX which is Philadelphia housing sector index yeah it's not a great chart at all it's not failing but it's definitely not acting very well so I want to put that together just to say this is the whippy time this is where as traders inter-day traders like we just looked at a moment ago is that not just a beautiful way of assessing strength and weakness that beautiful cup formation now it's starting to attempt the 39-27 level in the September E-mini one-minute chart so you can just go step-by-step but that's what I'm saying so I think that as a trading vehicle right now we're looking at maybe not getting a big core position of longs if you have and this is what I was saying to subscribers if you have portfolios you want to ensure that one of the reasons why we went short the Dow via the DOG back in the morning the 22nd of August there was because it just wanted that insurance it was way more important to have some insurance than to necessarily be trading but you can trade because that's just the nature of what we do for shorter-term people in the market so look at this Crude Oil is down 23 cents at 86.65 the more times we try to test the base you got a ceiling the more times you can push the ceiling you can eventually break it and on the base on the floor the more times you hit that floor the weaker it becomes well this is the base that we're looking at right now and it says that by next week there's a chance that Crude Oil takes out the support of the 15th of April of 83.93 that's the continuous contract remember and if that's taken out then the last support is 83.2020 that was made the week of the 6th to 18th of March once we below that it says you got to look at the weekly chart and say that looks like a dreaded age from the weekly chart that's that's impacting the monthly chart and that the 82 level the 200 period exponential moving average which since the Crude Oil broke above and that was the week of I think it was December of 2020 when it hit 34 after being at 28 it hasn't touched that 14 period moving average once twice but it hasn't broken under it that means all of a sudden Crude Oil now if that's the case then why isn't the IYT this is the Dow Jones I say Dow Jones Transportation Average Index Fund what a name just called it the index the Transportation Index is in a leg D to the downside in the daily chart the weekly chart is not all that good it's just flipping to at the start of a week so we can only say at the start of the week it's flipping to an S which is sell because the 9 is under the 14 and all I'm saying is that it's holding okay in the monthly chart but with Crude Oil pulling back like this we should have seen the better response in the IYT so with that said I'm going to just make it as clear as I can that this is selectivity you want to be in areas that are showing some kind of strength and if you can do that even then you want to find the strongest stocks in that particular sector now even more important than talking about stocks I wanted to show you something here with what impact stocks or what are stocks due to impact this particular index and that is the VIX the VIX ran to a higher high in leg E this morning it hit 2780 it's starting to pull back a little bit here and it wouldn't have surprised me at all if this week we find that the VIX is actually holding above the 2437 200 period exponential moving average but is dropping and holding kind of cities if fund managers are buying the volatility index as some kind of insurance or some kind of possibility of the markets being weak even on rallies I'll be back in a moment now David White is a powerful trading newsletter David White is an accomplished trader whose deep understanding of technology and markets allows him to consistently find and share winning trades support and resistance define the ranges in which stocks trade by understanding these trading ranges David White is able to find a path of least resistance David White's trading newsletter the path of least resistance is delivered daily before the markets open to make every trading day an easy win come today and subscribe to David White's ultimate trading newsletter for $119 a month and try all of our newsletters risk free with our 30-day money back guarantee take the path of least resistance at TFNN Educating Investors you might think that if you want to be successful at trading in the stock market you're going to need a crystal ball after all it's impossible to predict the future right like any endeavor in life before you decide it's impossible to predict the price from the experts you might find that it's not so impossible after all for daily market overviews that give you direction on the key indices selective stocks and commodities subscribe to the opening call newsletter at TFNN.com the opening call newsletter is written by Basil Chapman creator of the trading methodology known as the Chapman Wave the Chapman Wave up-down sequence gives you an edge in identifying price turns and valleys in stock prices get the opening call newsletter by Basil Chapman in your inbox every day first time subscribers also get a 30-day money back guarantee if you're not satisfied let us know and you'll get a full refund within 30 days of signing up TFNN.com Educating Investors everything in the universe is governed by the Fibonacci sequence this mathematical principle is responsible for everything from the most aesthetically pleasing artwork to patterns in the stock market to stay on top of stock patterns you can take advantage of sign up for the Fibonacci 24-7 newsletter at TFNN.com when you subscribe you'll get a weekly report from veteran day trader Larry Pezzavento on stocks you need to pay attention to and you can trust Larry's analysis after all he's got 45 years experience as a day trader Larry will also provide daily charts, videos and data on the key markets that he's tracking expect notifications from Larry on market movement you need to act on at any time first time subscribers also get a 30-day money back guarantee if you're not satisfied let us know and you'll get a full refund within 30 days of signing up subscribe to the Fibonacci 24-7 newsletter today TFNN.com Educating Investors on the front page of TFNN.com you can see it look he has the triple yield weekly that cup formation with the handle right now says it's a good chance we're going to pop above the high that was made does it get smoothed out? surely it's the same thing it should be 34-70 yes there should be a move above 34-72 and then at some point over the 2-3 weeks as it gets there and goes a little higher it should come back into the handle with the forest GTF look at that weekly chart that A uppercase A and it's starting to fade and it should come back to the 200-period moving average and even the high-grade sorry the Philadelphia housing index that A says yeah this is really important at 377 a close under 369 says uh oh failure pattern but I'm moving to the 383 sometime this week says no no if you're looking at different sectors look at the XLE trading at 79.46 down 51 cents made it peak D beautiful left side right side price time match in the Chapman wave methodology look here it is look at that that's to the high that I designated as a potential high and that was the candle of the 15th of June at 84.47 we're going to 84 85.18 just a 10 above and then came down so I think that the select energy spider fund can pull back and if a source of close under 70 a close under 77 suggests that that's going to be in the digester phase with the little guy to come back strong a little late don't provide that digester I'm going to hand it over to Steve Rhodes great programming all day I'll be back to come a little later today and check out more to come a day to say have a wonderful day


Organometallic chemistry is extensively used in catalysis for the synthesis of small molecules for large molecules like polymers and in day to day applications in the laboratory. However, one always wonders whether it can be used for other purposes and whether it has been used and this question is answered in today's lecture and presentation here. We will talk about some special properties and applications. In fact, the number of instances where organometallics have been used are quite large, but we will consider only a few of the topics like sensors, metal organic chemical vapour deposition and non-linear optics. So, let us start off with the special properties of ferrocene which make it really suited for electrochemical applications. If you remember the molecular orbital of ferrocene is such that the highest occupied molecular orbital is completely delocalized on the iron atom of the ferrocene. So, it is at the iron atom that the electron density is maximum in the ferrocene molecule and if you remove an electron it is the iron which is depleted of the electron primarily and it is in a non-bonding orbital, an orbital which is not interacting significantly with the cyclopentadienyl rings. In spite of that, we will see that there are some effects of the cyclopentadienyl ring, but this non-bonding nature of the highest occupied molecule orbital gives the iron atom tendency to have very little change when it goes from ferrocene to the ferrocenium cation. So, the ferrocenium cation which is pictured here has got very similar iron carbon distances, it has got very similar carbon carbon bond distances. So, it allows for reversible electron transfers and this property of reversibly transferring an electron to a molecule is possible only if the highest occupied molecule orbital is non-bonding and that is a completion ferrocene. You might always wonder so if it is not having changes in the bond distances and if it is going to be a reversible transfer, what is the use? If you recollect in electrochemistry, we usually use the standard Kalamel electrode as a reference point and in some systems where the standard Kalamel electrode cannot be used, it is necessary to use a secondary standard and ferrocene serves exactly that purpose. In many instances, ferrocene can be even used as an internal standard. That means during the course of electrochemistry, one can in fact add ferrocene into the solution, carry out the electrochemical experiment without ferrocene interfering with the processes that are going on. In other instances, ferrocene actually functions as an electrochemical catalyst. In other words, it permits the rapid transfer of an electron from say the electrode to the solution to the species in solution. So, this kind of a rapid electron transfer or the catalysis of the electron transfer is very important for electrochemical processes. On my right side, I have shown you couple of electrode potentials and all of them belong to the ferrocenium cation being reduced to the ferrocene neutral molecule in a variety of different solvents. You will notice that although there is a variation in this potential, as long as the solvent is kept reasonably constant. In other words, if it is not contaminated with water or very polar compound, this voltage is reasonably close to the value that is indicated here. So, one can be sure that ferrocene can be used as a secondary standard in electrochemical applications. I told you that there are some effects of the substituent on the cyclopentadienyl ring. Here, I have shown you four different molecules with respect to ferrocene, nem cation ferrocene. This electrode potential is marked as 0 volts because it is reference to this ferrocenium ferrocene couple. You will notice that if I add a very electron donating substituent such as a methyl group on the cyclopentadienyl ring, in this particular case, of course, we have added 10 methyl groups, 5 on the cyclopentadienyl ring on the top and 5 on the cyclopentadienyl ring on the bottom. Because we have added so many electron donating groups, this molecule becomes very difficult to reduce. So, it requires about minus 0.55 volts with respect to ferrocene to get reduced from the cationic species to the neutral species. So, here we are talking about a single electron transfer. Now, if you do a substitution on the ring with an electron withdrawing group as in the case that I have shown here, that is an acetyl group is added. Then of course, it becomes easier to add the electron. Now, this seems to be slightly contradicting what I started out with namely, the electron is completely localized from the ion and it is in a non-bonding orbital. And this would require that you have no changes in the electrode potential when you add or remove an electron withdrawing group. But nevertheless, you can see that there are changes, but all these changes happen to be in a reversible fashion. In other words, the acetyl ferrocene always has potential of 0.27 volts with respect to ferrocenium ferrocene cation coupled. So, if you make it the diacetyl group as I have indicated here, then of course, it becomes even more easy to pump an electron and it gets reduced at 0.49 volts with respect to ferrocenium ferrocene cation coupled. So, you can see that there are substituting effects, but they all are still reversible electron transfers. And one can depend on these chemical shift or electrode electrochemical potentials changing in a systematic fashion. So, this has been utilized for functionalizing an electrode. As I have shown you here, I have an electrode which is some many times a glassy carbon electrode which is attached to a cyclopentadienyl containing molecule. We talked all the while about the ferrocene, but it can be several cyclopentadienyl complexes. They can be half sandwich complexes as I have indicated here or this cyclopentadienyl sandwich complexes as I have shown on the left hand side. So, if I have acetylide moiety attached to the cyclopentadienyl ring, then depending on the group that is there on the terminal position of the cyclopentadienyl group, it can be oxidized and oxidatively coupled to the glassy carbon electrode. This has been very recently shown to be a easy method for functionalizing the glassy carbon electrode. So, this is a glassy carbon electrode which is generally an inert electrode where you can carry out electron transfers, but the transfer itself has a high barrier. But when you attach an organometallic moiety as I have shown here, then the electron transfer between the reduced and the oxidized species. The reduced and the oxidized species transfer electrons to the organometallic species and so transfer the electron to the glassy carbon electrode. So, this transfer turns out to be a very facile transfer and the electrochemical reaction is facilitated because of the functionalized electrode. Now, this is exactly the principle on which the glucose sensor for example, has been designed. These are amperometric sensors. In other words, they measure the current flow that is there in the electrochemical setup in order to detect the presence of a species and to quantify the species. So, you have an enzyme which specifically oxidizes glucose, but the enzyme itself is not capable of transferring that electron to the electrode. So, you need a modified electrode and the electrode is modified using ferrocene substituted species. This is what is allowing Claremont and co-workers to even develop an implantable version of a glucose sensor which would be extremely useful of course for patients suffering from diabetes. They would have real time monitoring of the glucose in the blood. So, this is possible because you can have an electrode which is functionalized with say ferrocene or a substituent of a ferrocene and the glucose is oxidized, glucose oxidized enzyme oxidizes the glucose to a gluconolactone. And this gluconolactone when it is formed it releases two electrons and these two electrons are now transferred to the enzyme. The enzyme in turn transfers it to the electrode, but a direct transfer turns out to be difficult and it is the ferrocene which is attached to the glassy carbon electrode or a suitable electrode is a one which is necessary for conveying this electron from the enzyme to the electrode. So, you have a very easy way of measuring the amount of glucose that is present in the system using this type of an electrochemical setup. Normally one usually one measures the current that is being generated as a result of this electrochemical reaction and this is conveniently monitored. Now, you can you might have realized that if I can use ferrocene as a catalyst for an electrochemical reaction it must be a way of coating this electrode with the organometallic species. And one can use a single molecule functionalized and coated on to the electrode or one can think of polymers which are either polymers because they connected through the organic ligand that is a cyclopentadienyl ligand that is present on the ion or one can think of connecting it through the metal in other words is it possible for us to generate a polymeric species where the metal atoms are linked one after the other. So, here I have shown for you some organometallic polymers and these organometallic polymers are generated in a couple of different ways. In the first in this first example that I have shown to you there is a unique way of linking the polymers and that is what is called a ring opening polymerization it is analogous to the ring opening polymerization. But in this case it is it is assisted by the strain that is caused when you link two cyclopentadienyl rings through a very small bridge. So, this bridge opens up and when this bridge opens up it can link to another molecule in such a way that you can release the strain. And so the strain that was there because of this acute angle which should have been 180 degrees and it is made acute because of the bridge when a ring opens you end up with a very nice polymeric species where there is no strain. And ferrocene is linked to another molecule to another molecule of the ferrocene in a nice chain. So, this is the chain that is generated and this chain propagates. Now, what is the advantage of such a system? You have a processable polymer and this polymer can be now coated on to the electron. And so it forms an electro catalyst which can reversibly transfer electrons. And the transfer between these two systems also is reasonably facile. So, that one can have a very nice electro chemical reactions. Now, this transfer of an electron from one ion atom to the other although I have presented it as if it is very easy. It is not always a completely reversible electron transfer. And the system where it is completely reversible is the bisphylvalene diion. This is shown here. This is called the bisphylvalene diion molecule where the two cyclopentadienyl units are directly conjugated. And if you if both ion atoms are linked through both cyclopentadienyl rings then it forms a completely delocalized system. So, much so the oxidation state of each ion atom is 2.5. And no property of the ion atom distinguishes it as a plus 3 and plus 2 unit. They are completely delocalized and completely equivalent in any time scale that you can think of. So, it is not as if an electron is hopping back and forth. It is the electron is sitting in a delocalized molecular orbital on the two ion atoms. Now, the molecular weights of these molecules when they are linked directly to each other turns out to be reasonably small. But molecules like this species can be fairly large. They can be as high as 10 power 5 to 10 power 7 voltants. And still the electrochemical properties of these molecules are maintained and they are weak semi conducting polymers. So, in other words these organometallic polymers are useful species. They turn out to be extremely valuable for electro chemically coating some electrodes. And also in some specialty applications where you need a conducting surface for a particular application. Here is another way a second way which I wanted to illustrate for making an organometallic polymer. In this instance you have a molecule which is a sandwich structure. But the sandwich structure has two different types of breads on either side of the metal atom which is in the center. Because you have a aromatic ring the aromatic ring has got two chlorine atoms. And you will remember that because of electron withdrawal from the aromatic ring it is now possible to carry out nucleophilic substitution of the aromatic ring with the phenoxy group. So, any nucleophile will do. But if you have a phenol which is a diol then a bis phenolic compound can do substitution with two different molecules of the ruthenosine which is now a polymeric species. Because you are going to repeat this unit several times. And so you have a nice processable polymer which is linked directly which is linking directly two different ruthenosine atoms or entities. So, this kind of substitution reaction turns out to be extremely useful. And it can be used for several applications in electrochemistry. When it comes to very small small say when it comes to an application which requires a very small contact people have been thinking about making molecular wires. In other words if I attach two electrodes through only a single molecular entity then I can have a molecular wire. But very often these single molecules do not conduct electricity and they turn out to be very poor conductors. One of the early studies which successfully made a molecule which almost look like a molecular wire starts out with a platinum two species which is a cyanocomplex. Although we do not consider this entity as strictly as an organometallic compound it illustrates the purpose for it illustrates the principle that we are talking about and that is the making of a molecular conductor. So, this platinum two plus unit can be partially oxidized with bromine to generate this oxidized species which turns out to be extremely interesting. Here is the oxidized species and here is the neutral species. The neutral species the platinum the p t c n 4 2 minus units are separated by 3.3 angstroms. The distance is significantly reduced when you oxidize the platinum. Oxidization of the platinum leads to shorter platinum-platinum interactions. This distance turns out to be reduced significantly and that has been attributed to removal of electron density from a d z square orbital which is along this axis. So, removal of an electron from this axis and formation of a platinum-platinum bond along this axis leads to the formation of a molecular conductor because it is only going to be a half filled orbital. Both electrons are not removed this is a partial oxidation and this gives you exactly the features of a conducting material. Turns out that this can be made with a variety of different oxidants with platinum oxidized in such a way that the anionic species is not there, but the cation is present in a non stoichiometric amount. Whatever be the procedure you end up with a copper colored a metal colored compound which has got a reasonably high conductivity. Of course, this does not have the good properties of the polymer that we talked about earlier, but nevertheless this is a molecular wire because the conduction is extremely high along this axis and this conductivity is also anisotropic. Very clear indication of the fact that it is delocalization of the electrons on the platinum along one particular axis. Now, in a very dramatic development recently, palladium molecular wires have been made. Now, turns out that platinum turns out that platinum was the only example where such an molecular wire was made and here for the first time palladium has been utilized to make a molecular wire. Once again palladium 2 plus complex is a complex you start out with and these molecules are pictured on the top. These are discrete molecules. They are stacked, but nevertheless they are not aligned with each other in the solid state. So, they are palladium 2 plus complexes, but if you oxidize them a very strange thing happens. A palladium palladium bond happen is formed just like you have in the case of the platinum. Now, there are two different things that are happening. One is that the aromatic ligands which are interacting with the palladium align themselves and also the palladium atoms are aligned so much so that this compound is likely to be a semiconductor or a conductor at best. Let us take a look at the oxidation reactions that have been carried out. This was an interesting case of a dinuclear system undergoing oxidative addition when the researchers Tobias Ritter used PHICL 2. PHICL 2 has a tendency to become PHI, PHI and the CL 2 oxidizes the palladium. During the course of this oxidation each palladium atom which was originally a palladium 2 plus center became a palladium 3 plus center, but because there are two electrons coming from the two chlorines you have both palladiums oxidize to palladium 3 plus center. You will notice that there is a palladium carbon bond in this molecule. So, that accounts for the second source of electrons for this molecule. So, you have palladium 2 plus to begin with and then you have three anionic ligands. So, you have a palladium 3 plus dinuclear oxidized center and surprisingly this molecule when you heat it, it only gives you a reductive elimination where this chlorine is removed along with this palladium along with breakage of this palladium carbon bond and formation of a chlorine carbon bond which gives you this molecule two units of this molecule. So, this is the case of a simple oxidative addition and a reductive elimination. Surprisingly when the when the workers used researchers used xenon fluoride, they formed this very interesting molecule which had counter ions of fluoride which is what you would expect, but a very strange alignment of the palladiums and the formation of a palladium palladium bond. This palladium palladium bond is close to 600 atoms long in the crystals that are available. They are so long that they are long needle like crystals which are metallic above 200 k and it is very clear that there is delocalization of the palladium deorbitals in such a way that you have this nice molecular conductor being generated because of this orientation. So, this is the same molecule that we showed you earlier and here it is shown as a line diagram. Now, let us move on from electrical properties to electronic properties of organometallics. The optical properties of organometallics are very similar to the optical properties of many organic compounds. More often than not materials respond to light in a linear fashion. If you have a light falling on a molecule, the molecule scatters the light and that light comes out with a lower intensity. It also transmits the light and that also comes out with a lower intensity because some of the light, some of the photons are absorbed by the molecule if they have the right energy to excite an electron from the ground state to the excited state. In some instances, in a few instances when you can have excitation, the excited electron coming back to the ground state, you can have fluorescence or phosphorescence. Because there are some changes in the vibrational states of the excited state molecule, you do have changes in the wavelength of the light. Usually, the light that comes out is of a longer wavelength. So, in most properties that you observe for molecules, the incident light's frequency and the light that is transmitted or scattered is usually of the same wavelength or of a longer wavelength. There are very few instances where molecules interact with the light in a non-linear fashion. And here also the intensity of the light that is coming out is of a lower intensity, but it turns out to be half the wavelength of the light that is incident on the molecule. Now, as the energy is inversely proportional to the wavelength, you will notice that the light that is coming out is of a higher energy than the light that is coming in. And so, the intensity obviously this can happen if you have two photons coming in and both photons have interacted in such a way in the molecule such that lower wavelength or more energy containing photon is coming out from the molecule. During these processes, all the other processes that we talked about, fluorescence, transmittance of light, etcetera, all of them scattering of light, all of them are happening. But in addition to these properties, you have this non-linear response. Now, this non-linear response is very interesting because you can use light of a low wavelength to convert it to a light of even smaller wavelength, but higher energy. So, this turns out to be very interesting and one has to maximize it and the whole race or the challenge is to maximize it and the intensity of this half wavelength light that is coming out. So, how does one do it? People have been working on this particular property for a long time now and a few simple thumb rules can be derived from what is called a two state model. According to the two state model, it is the difference in the dipole moment between the ground state and the excited state that is important. So, can we manipulate organometallic molecules such that they have a very large change in the dipole moment? This can be done with organic molecules also and it has been done and what one can do with organometallic molecules however is slightly different and that is what we are going to talk about. A second point that one has to note is that in the solid state, it should not be a centrosymmetric solid which will result in cancellation of these dipole moments and result in a zero response for the non-linear optical property. So, this non-linear optical property is measured as the coefficient beta and if the incident light is having a wavelength of 1064 nanometers it is indicated as a superscript because the non-linear response is dependent on the wavelength of the light that is coming in. So, if you have a 1064 nanometer light the beta value would be different from what you have if you have a 532 nanometer light that is coming in. Usually these measurements are made with high powered lasers because the intensity of the low wavelength high energy light that is coming out is reasonably small. So, you need a laser in order to measure the wavelength of intensity and wavelength of the light that is coming out. So, here are two molecules and the first principle that one can see is that when you increase the conjugation and the conjugation has been increased by adding this typhoon group. So, you have one typhoon group here, here you have two typhoon groups and you will notice you have two different groups. We will make it a donor and an acceptor. So, this donor acceptor units are separated by a larger distance in this molecule and that leads to a larger value for the non-linear response. So, you can see that this is just one example, but a multitude of examples can be given where it is very clear that if one increases the conjugation between the donor and the acceptor then it is possible to increase the non-linear response in the molecule. The second principle that is clear is that if one has a better acceptor or a better donor it is possible to have a better non-linear response. I am again illustrating it with a similar molecule, but you will notice that there is a tremendous increase in the non-linear optical property by attaching a molecule next to the Sino group which makes the Sino group a better acceptor. So, this is an acceptor to start with, but this acceptor is much better. So, because of the increase in the accepting property of the ferrocene half sandwich that is attached here, you have been able to increase the non-linear response by more than 2 fold close to 3 fold increase in the non-linear response has been achieved. So, these are two simple principles which I have shown to you using organometallic examples, but it is clear that some generalizations can be made on the basis of a large number of studies that have been done. Firstly, conjugation can be increased in order to achieve larger non-linear response and this is increased very readily in organometallic molecules. Secondly, they have to be stable because high intensity lasers come in and so if the molecules are not very stable on heating, they can decompose and you lose the response. So, far the best molecule or the unit that has been found to be a donor has been this bis diphenyl phosphinoethane moiety attached to a ruthenium center and the donors are better as you go down the group. It is also possible that donor acceptor properties can be changed by oxidation that is one advantage in an organometallic non-linear optical material because you can make molecular switches by reducing and oxidizing the ruthenium center. You would be changing the redox properties of the molecule in question. Now, in general a 3D transition metal is better than a 4D or a 5D transition metal and because you can polarize the 4D and 5D transition metals, one would have expected the opposite to be true, but in general it has been found the 3D transition metals are better. So, the organometallic compounds provide a very clear advantage for making new non-linear optical materials and this has been reviewed several times in the recent literature. Now, we proceed to properties of materials other properties of materials and let us take a look at how some materials are made using chemical vapor deposition. This is a root which is used to make for example, titanium nitride which is a gold colored compound it can be used for coating watches or ornaments and they may look like gold, but they are not really gold and this material titanium nitride is extremely hard it is conducting it looks very much like a metal. But unfortunately if you want to coat a metal or a material with titanium nitride it is not easy to carry out that process because it is not a volatile compound, but you can take an organometallic compound which is volatile. So, you take a volatile organometallic compound and then you decompose it on a substrate leaving behind the desired material which is a metal or a metal nitride a carbide or an oxide. All these possibilities are have been realized and the trick is to use an organometallic compound where the metal x bond whether it is to nitrogen or to carbon or to oxygen the metal x bond has to be weak. You can generate the desired species on the substrate and if you have reasonably easy ways of decomposing the material then the kinetic parameters are suitable for carrying out metal organic chemical vapor deposition and you do not have a very high temperature that is required for carrying out this chemical vapor deposition. The advantage of chemical vapor deposition is that you need very little post processing of the material and if you can make a molecule which has got both metal and nitrogen metal and carbon then you can have what is called a single source precursor for carrying out the cycle of chemical vapor deposition. This turns out to be an extremely useful parameter because if you have two different process materials giving you the metal and giving you the nitrogen then the processes for the required for controlling the two molecules at the substrate become very difficult So, let us take a look at metals if you want to deposit a metal for example you could take a metal allylic complex. These metal allylic complexes have got a very easy decomposition route they undergo reductive elimination of the two allyl groups and form this 1, 5 hexadiene. So, these are 1, 5 hexadienes so you can see that they are 1, 5 hexadienes and they are easily formed on decomposition of a divalent metal allylic complex. These species even if there are other l n molecules they turn out to be reasonably volatile. So, at very low temperatures you can volatilize this precursor and in a substrate which is kept hot it undergoes decomposition and deposits the metal in a pure form because this molecule is volatile it will be lost very readily and you end up with the deposited material which is in a pure state. One can not only use metal allyls one can even use metal alkyl species and in this case the decomposition might be slightly more complex. You can have a variety of decomposition routes you can have the ethyl group here. This ethyl group reacting with one of the hydrogens here and giving you ethane and an olefin complex and in a subsequent step the olefin might be lost and the metal might be deposited on the substrate. In another scenario one can also think of decomposing the molecule in such a way that the 2 ethyl groups are attached to each other and bond is formed and butane is eliminated. So, either way it is easy to make metals on top of a substrate using chemical vapor deposition of metal alkyl compounds. Here is a schematic representation of how one would do this reaction or how one would carry out. You can have this metal alkyl species sitting in a container which is volatilized using some heat and sometimes it is also nebulized using an inert gas and this carries this material on to a glass tube where the substrate is kept. A simple substrate would be a quartz substrate and usually this kept hot the temperature of this furnace is kept at a temperature above the temperature at which this material would decompose. So, it decomposes only here the organometallic species decomposes at this point deposits the metal on top of the substrate and the organic compounds are pumped out and the liquid nitrogen traps collect the volatiles and the organic compounds that come out. The whole thing is kept under high vacuum usually and in such a way that the organic species do not stay in the region where you want to have pure metal deposited on the substrate. Here is an example where you have some semiconductors made these semiconductors are called 3 5 semiconductors or 2 4 semiconductors and many of them have been made or deposited on a substrate using this chemical vapor deposition method. The temperatures are rather high it is about 600 degrees, but relatively lower than what you would end up with if you had to use a completely inorganic route for making these molecules or making these alloys. So, here is a gallium arsenide deposition using trimethyl gallium which is an organometallic species. You can also have a single source precursor which I was telling you about where there is a gallium arsenide bond and you can vaporize this gallium arsenide bond directly on to the substrate and deposit the required amount of gallium arsenide. The advantage of using a single source precursor over a 2 source precursor is that the vapor pressures of these 2 molecules are different and as a result it would be very difficult to adjust the amounts of gallium and arsenide and you should not end up with excess of arsenic or excess of gallium on the substrate. So, to avoid that a single source precursor is always preferred. One can also dope for example, here in the case of indium phosphide one has doped it with a terbium and this terbium is delivered as a cyclopentadienyl complex. So, once again you see that an organometallic lanthanide, organo lanthanide is used in order to dope the semiconductor appropriately. So, it terbium terbium have all been used as dopants and as organometallic precursors and here is a 2, 4 semiconductor which is also generated using an organometallic compound. So, you can see that chemical vapor deposition is a very useful tool. It can be used for generating a wide range of semiconductors both in the pure form and in the doped form. In order to make a metal oxide or a metal nitride, one can also use what is called plasma enhanced chemical vapor deposition, where there is a plasma which is which contains a reactive gas and in this plasma the chemical decomposes and this leads to the appropriate deposition of the appropriate material. This is also being found and it has been utilized very advantageously. In most of these cases that we have talked about today, organometallic compounds are used as materials and in some instances in recent times it has been used as a catalyst for making a material. In other words the organometallic itself is not part of the material that is formed, but it is used in very small amounts. So, that the material is generated in a pure form and in a useful material is generated. There is another example where a carbene has been used as a catalyst. This is an organic compound. This organic compound has been used as a catalyst for an organometallic reaction. So, this is the inverse of what we have been seeing so far. We have been using organometallic catalysts from carrying out organic reactions. Now, we are going to talk about two examples where organometallic compounds are used as catalysts in very unique ways. The first instance that I want to talk about is a single wall carbon nanotube. Single wall carbon nanotube is often formed by something very close to the chemical vapor deposition that I talked about. It is conducted by pyrolysis of carbon rich compounds. When you pyrolyse the carbon rich compound you lose hydrogen and generate a carbon network which is like a tube. So, this is a carbon nanotube and multiple tubes are formed. What is interesting is that the best catalyst that is available for making this carbon nanotube especially single walled carbon nanotube is ferrosine which is this organometallic molecule. Let us see why this is the case. If you look at a piece of a carbon nanotube very often it is indicated as a series of hexagons which are connected with each other. Here is a long picture of a long carbon nanotube, single walled carbon nanotube that is shown for you here. Here is another picture which is dynamic but you can see that the carbon nanotube is primarily made up of hexagons which are connected with each other. Now, there are different types of carbon nanotubes and these nanotubes have got different conducting properties different properties which have been utilized for different applications. But in most of the nanotubes you will notice that it is the 6 membered ring which is being linked to one another. So, how are these carbon nanotubes attached to or how are these hexagons attached to each other and how are they formed in the first place. Although we indicate carbon nanotubes the middle part of the nanotubes what we do not realize is that the end of the nanotube there is in fact a cup that is attached. It is this cup that is responsible for the formation of this nanotube. In other words the cup is formed first and then the nanotube propagates along this direction growing along this direction. So, the cup is of great importance if you cannot make the cup then you cannot make the nanotube. So, let us take a closer look at this cup that we are talking about. It is often called a cap for the nanotube and here is how one thinks about making the carbon nanotube. If you have acetylene as the source for the carbon required for making the carbon nanotube you can think of capping or attaching three benzene rings around the cyclopentadiene ring. If you use only benzene rings it would not be possible to make the curved cup formed at the end of the nanotube. So, if you have a cyclopentadiene ring however you can attach three C 6 units around it to form this curved molecule. Although we have drawn it in a flat two dimensional form you can see how this molecule will be curved. We think of the fact that it is not possible to keep all five carbon atoms in a plane when you have only a single double bond inside the ring. So, let us take a look at what would happen. If you attach some more cyclopentadiene rings to this final structure and you will now understand why one needs ferrocene because ferrocene supplies this five membered ring which is not accessible when you use only acetylene as a source for the carbon. So, ferrocene turns out to be an excellent catalyst because to form this initial curved structure that we have indicated here it is important to have a nucleating center and that nucleating center comes from this cyclopentadiene ring of the ferrocene. Once it is formed of course it keeps growing and that is what is shown here schematically. First the formation of the cup is indicated and that happens by combining two or three units of this cyclopentadiene containing ring structures which are surrounded by C 6 H 6 units and then the hydrogens are lost and then again you end up with a curved structure which can now propagate in a linear fashion. So the cap is all essential for forming the nanotube and so that is why carbon nanotubes are mostly formed using ferrocene as a catalyst. Now, I will come to one other example where an organic catalyst has been discovered for an organometallic reaction. Although this is a novelty at the moment the principle behind this whole discovery is very important and that is if you have a molecule which can both give and take electrons give and protons then that molecule will be a good catalyst. Now, organometallic molecules were good catalyst because they could both accept electrons into vacant orbitals and give electrons into the anti-bonding orbitals of organic molecules. By doing so they facilitated many electron, electronic structure changes on the molecule or in other words reactions. Now, if you look at a carbene, a carbene has got if it is a carbene such as what is shown here then it has got a pair of electrons which it can donate but at the same time perpendicular to the pair of electrons you have a vacant orbital which can accept electron density. So, as a result carbene can function very similar to organometallic molecules and they can be catalyst and in this example it so happens that they are catalyzing an organometallic reaction. The organometallic reaction that has happened is a conversion of biscyclo octatetraenyl ion which is basically ion coordinated to two cyclo octatetraen units. In one case it will be three double bonds coordinated to it in the other case the ring is different only two other double bonds would be coordinated to it. Now, we have indicated an A here to show that there are two different ion atoms that are going to react. So, initially you have FeA and then a second molecule of the cyclo octatetraen complex comes in and that is labeled as FeB. So, there are two sources for the ion in the dinuclear complex and a dinuclear intermediate is formed. This molecule in which there is a carbene attached to an ion and two cyclo octatetraen units attached to the second ion atom is an intermediate it has also been isolated and characterized. The beauty of the study was that in most cases it was possible for them to show the NMR of the compound and also characterize some of the intermediates using X-ray crystallography. And the compound that they finally isolated as the most stable or the majority of the species was a tri ion tricyclo octatetraenyl compound. And this molecule is got a beautiful structure where it adopts 6 pointed star kind of a structure and you have a first organometallic cluster which does not have carbon monoxide.  And this compound has got an unusual oxidation state you can see that the ion is in fact attached each ion is attached to a 5 carbon unit and a 3 carbon unit. You started out with a neutral species, but by oxidative coupling you have in fact oxidized the ion and coupled 3 cyclo octatetraenyl units in such a way that ion now has a formal oxidation state of plus 2. So, let us take a look at this 6 pointed star. Here is a 6 pointed star that I was telling you about it is a very beautiful structure that we will look at in a 3 dimensional fashion to appreciate the beauty of this molecule. Here is a molecule in 3 dimensions and you can see that each ion atom is coordinated to either 5 carbons on one side. Here are the 5 carbons that are interacting with the ion and on the lower side you will see that the same ion atom is interacting with only 3 carbons. So, on one side it has got 3 carbons and on the other side it has got 5 carbons. And if you look at it and through this axis you will notice that it forms a 6 pointed star structure. So, this beautiful molecule is in fact formed by interacting an organic molecule with an organometallic species. And it is the organic catalyst which generates this molecule very efficiently. In fact this whole reaction can be carried out in 95 percent yield with a turnover number of 9.5 with this n heterocyclic carbene. What is interesting is that this all the intermediates several of the intermediates have been characterized using variations in the structure of the alkyl groups which are attached to the nitrogen. So, here is a proposed catalytic cycle which just involves loss of cyclo octatetraene in a sequential fashion formation of an ion ion bond and the formation of the trinuclear intermediate. So, here are two intermediates which have been isolated and these are available in the Cambridge structure database. And in one case you have an ion atom which is coordinated to a carbons. And two cyclo octatetraenes and that is this molecule and in other case you have a molecule which is coordinated to two of these carbene units at the same time. So, that is this molecule which is shown here. So, with this let me conclude by saying that materials for making new organometallic materials can be used in a variety of ways very very organometallic compounds can be used as materials and also for generating new materials. The advantage of organometallic compounds is that they are accessible easily accessible easily made and they can be tailor made to function in a particular way. And this is because they can be easily functionalized any of these organic ligands can be converted to new ligands and new molecules can be generated. And to top it all they are extremely affordable which is also important when you are thinking of making new materials. Finally, let me conclude by talking about organometallics in general. We have talked about a variety of systems where organometallics have been used for organic synthesis. They are useful for making new molecules, new drugs, new molecules for materials and in the biological science also for both for diagnosis and for therapy. But in all these cases the advantages of the organometallic compounds make them fairly unique. You have the redox properties of the metal atom which you can play around with. You also have the organic structure which you can change very readily. Where are we going? Well it is now possible to have systems where you can have domino reactions which means you combine two different organometallic catalysts in such a way that you carry out a reaction. In a single pot you carry out two different reactions sequentially. So, these are called domino reactions and these domino reactions are possible because of organometallic compounds which are behaving as catalysts. This also leads to new reactions which have not been known earlier. In this lecture, in this series of lectures we have only considered some of the very basic and simple lectures, simple reactions that are possible with organometallic compounds. Finally, of course, asymmetric catalysis is an extremely important project that is ahead of the organometallic chemist. In order to make chiral molecules very efficiently, it is important to use chiral ligands and asymmetric catalysis will play a very important role in organometallic chemistry in the future also.