Lewis acid group 14 organometallics

Hydroboration of Organometallic Alkenes. A transition metal compound containing a ligand that combines both an Tj-arene 7r-donor group and a boron cr-acceptor (Lewis acid) group has been successfully prepared by the hydroboration of an alkene bearing j-arene derivative of chromium (eq 14). ... 

Applications involving ring transfer or loss. The kinetic lability, volatility, and Lewis acidity of heavy alkaline earth metallocenes have been the properties most important to their applications. The gas-phase decomposition of volatile metallocenes is useful in the preparation of thin films of alkaline earth-containing materials and in doping semiconductors. Reviews are available on the use of group 2 organometallic compounds as precursors for chemical-vapour deposition (CVD).2 3... 

The formation of the heterocycle 1 from the xylylene-bis-phosphonium salt 2 and PCI3 proceeds via a detectable intermediate 3 in a cascade of condensation reactions that is terminated by spontaneous heterolysis of the last remaining P-Cl bond in a cyclic bis-ylide-substituted chlorophosphine formed (Scheme 1) [15]. The reaction scheme is applicable to an arsenic analogue of 1 [15] and to bis-phosphonio-benzophospholides with different triaryl-, aryl-alkyl- and aryl-vinyl-phosphonio groups [16, 18, 19], but failed for trialkylphosphonio-substituted cations here, insufficient acidity prohibited obviously quantitative deprotonation of the phosphonium salts, and only mixtures of products with unreacted starting materials were obtained [19]. The cations were isolated as chloride or bromide salts, but conversion of the anions by complexation with Lewis-acids or metathesis was easily feasible [16, 18, 19] and even salts with organometallic anions ([Co(CO)4] , [CpM(CO)3] (M=Mo, W) were accessible [20]. 

Owing to the high Lewis acidity the group 14 organometallic cations are polymerization catalysts par excellence. so Silanorbonyl cations and triethylsilyl arenium have been shown to be efficient catalysts for metal-free hydrosilylation reactions. Chiral silyl cation complexes with acetonitrile have been applied as cata -lysts in Diels Alder-type cyclization reactions °792 intramolecularly stabilized tetracoordinated silyl cations have been successfully used as efficient catalysts in Mukaiyama-type aldol reactions. 

A major limitation of such Group IVB metallocene catalysts is that they are air- and moisture-sensitive and not tolerant to heteroatom-containing monomers. In the case of heteroatom-containing monomers the unbonded electron pairs on the heteroatom, such as oxygen, preferentially coordinate to the Lewis acid metal center in place of the carbon-carbon double bond. Some so-called middle and late transition metal organometallics are more tolerant to the presence of such heteroatoms and can be used as effective cocatalysts. These include some palladium, iron, cobalt, and nickel initiators. 

Many catalysts do not use metals in their pure reduced metallic forms. Anchored organometallic complexes are often analogs of homogenous catalysts fixed on a solid support. In particular, titanate complexes both in solution and in supported form have been found to be especially active in transesterifications of simple esters.It was proposed that titanates catalyze the transesterification reaction through a Lewis acid mechanism where the reactant ester and metal form a Lewis complex activating the carbonyl groups for a nucleophilic attack by the reactant alcohol. The tetrahedral intermediate that is formed breaks down into the product alcohol and an ester-metal Lewis... 

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