Hydrides reactions with metal silyls

Previous investigations of the photolysis reactions of 5 in the presence of various silanes only showed the products of Si-H activation [20], Metal silyl hydride formation, however, becomes the main reaction path with sterically less hindered silanes [21]. 

Silicon and germanium hydrides react with cobalt, manganese and rhenium carbonyls affording complexes having a silicon (or germanium)-metal bond. These reactions, described previously for inactive compounds have been used in the synthesis of optically active silyl and germyl-transition metals ... 

Rhodium carbonyl complexes also catalyze the cascade cyclization/hydrosilylation of 6-dodecene-l,l 1-diynes to form silylated tethered 2,2 -dimethylenebicyclopentanes. For example, reaction of ( )-85 with dimethylphenylsilane catalyzed by Rh(acac)(CO)2 in toluene at 50 °G under GO (1 atm) gave 86a in 55% yield as a single diastereomer (Equation (56)). Rhodium-catalyzed caseade cyclization/hydrosilylation of enediynes was stereospecific, and reaction of (Z)-85 under the conditions noted above gave 86b in 50% yield as a single diastereomer (Equation (57)). Rhodium(i)-catalyzed cascade cyclization/hydrosilylation of 6-dodecene-1,11-diynes was proposed to occur via silyl-metallation of one of the terminal G=G bonds of the enediyne with a silyl-Rh(iii) hydride complex, followed by two sequential intramolecular carbometallations and G-H reductive elimination. ... 

Reaction with Further Electrophiles of Group IVA (Sl,Ge,Sn). IV-Silylated aziridines can be prepared from ethyleneimine by amination of chlorosilanes in the presence of an HC1 acceptor, by dehydrocondensation with an organosilicon hydride or by cleavage of a silicon—carbon bond in 2-furyl-, 2-thienyl-, benzyl-, or allylsilanes in the presence of an alkali metal catalyst (262—266). N-Silylated aziridines can react with carboxylic anhydrides to give acylated aziridines, eg, A/-acetylaziridine [460-07-1] in high yields (267). At high temperatures, A/-silylaziridines can be dimerized to piperazines (268). Aldehydes can be inserted... 

The proposed catalytic cycle for this unique process includes (i) oxidative addition of a hydrosilane to [Ru—CO] species to form (R3Si)(H)Ru complex 369, (ii) silyl migration to generate siloxycarbyne-Ru species 370, (iii) carbyne reaction with CO to form metal-lacyclopropanone 371, (iv) hydride shift to generate oxyacetylene-Ru complex 372 and... 

Alkyl carbonyl substrates turn out to be more reactive when stabilized in the cnolic form cither as silyl enolethcrs 4, obtained by reaction with (CH.O.iSiCl,- or as metal enolatcs 5, usually produced by lithium alkyls, lithium amides, or hydrides starting, for instance, from cnolcthers <>i... 

The discovery of the hydrosilation reaction has greatly stimulated research on transition metal-silyl complexes. Currently, there are examples of silyl complexes with almost every transition rnetal. " Silyl hydride complexes are of special interest with respect to the chemistry of the hydrosilation reactions. Such compounds can be seen as the products of oxidative addition into the Si-H bond and thus are intermediates in hydrosilation reactions following the ChaUc-Harrod mechanism. 

The (dienyl)iron cations of type (248) and (265) are susceptible to reaction with nucleophiles. For the (cyclohexadienyl)iron cations, nucleophilic attack always occurs at a terminal carbon, on the face of the ligand opposite to the metal, to afford / -cyclohexadiene products. Typical nucleophiles used are malonate anions, amines, electron-rich aromatics, silyl ketene acetals, enamines, hydrides, and aUyl silanes intramolecular nucleophilic addition is also possible. The addition of highly basic organometaUic nucleophiles (Grignard reagents, organolithiums) is often problematic this may be overcome by replacing one of the iron carbonyl... 

The alkali metal hydrides NaH and KH are also effective as metalating reagents for hydrosilane and disilane to give trialkylsilyl anions in an aprotic solvent such as THE, DME, or HMPA 8) (Scheme 4) (for the mechanism, see Section III-A-2). The reaction of disilane with 2 equivalents of metal hydride converts both silyl groups into silyl anions in two steps, in contrast to the reaction with MeOM described earlier. 

An interesting synthesis of silyl enol ethers involves chain extension of an aldehyde. Aldehydes are converted to the silyl enol ether of a ketone upon reaction with lithium (trimethylsilyl)diazomethane and then a drrhodium catalyst. Initial reaction of lithium(trimethylsilyl)diazomethane [LTMSD, prepared in situ by reaction of butyllithium with (trimethylsilyl)diazomethane] to the aldehyde (e.g., 37) gave the alkoxide addition product. Protonation, and then capture by a transition-metal catalyst, and a 1,2-hydride migration gave the silyl enol ether, 38. 

Treatment of tantalum hydride complexes with hexamethylsilacyclopropane at 65 °C in the presence of a Lewis base gave the corresponding silyl-tantalum compounds in excellent yield. It appears that this reaction takes place via direct insertion of dimethylsilylene into the tantalum-hydride bond, which would make it the first example of silylene trapping by a transition-metal substrate (Equation (15)) <87JA6210>. 

The mechanism and stereochemistry of reactions with transition metals. In connection with the mechanism of hydrosilylation reactions, it is of interest to discuss the stereochemistry of silyl-transition metal complexes (12) and the stereochemical aspects of the reactions of silicon hydrides with transition metals. 

The reaction of metal carbonyl dimers with silicon hydrides also probably involves an initial oxidative addition step. Chiral silyl-cobalt and silyl-manganese carbonyl complexes have been obtained through the reaction of optically active organosilicon hydrides with metal carbonyls65 68 (equation 15 and 16). Phosphine-substituted cobalt complexes were similarly obtained by reaction of a chiral hydrosilane with Co2(CO)6L2 [L = PPh3, P(OPh)3, P(c-C6Hn)3]69. 

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