Download Comprehensive Handbook on Hydrosilylation by B. Marciniec PDF

By B. Marciniec

This guide offers an up to date account of hydrosilylation reactions and the instructions within which man made and mechanistic reports in addition to functional purposes of those techniques are continuing. The publication comprises components: the 1st is descriptive, proposing the catalytic, mechanistic, structural and artificial elements of hydrosilylation, in addition to its software in natural and organosilicon chemistry. the second one half, awarded in tabular shape units out encyclopedic details pertaining to response stipulations taken from greater than 2000 papers and patents within the interval 1965 - 1990

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Extra info for Comprehensive Handbook on Hydrosilylation

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Some reactions mentioned above are useful in the search for novel and efficient synthetic methods, and for this reason require separate consideration. Although many transition metal complexes catalysed olefin isomerization, early studies showed that the presence of silane markedly affects such reactions which occur concurrently with hydrosilylation. l7]. 38 COMPREHENSIVE HANDBOOK ON HYDROSILYLATION CH2 R C H 2C H 2C H 2 H I CH2 I CH—M—Si= Si= CH2 I R (tf 2-complex) ÇH ÇH2 ((^-complex) R (jz^-complex) ^ CH2 H 1 // HC M—Si== V I CH H H I CH2 2 I Si= CH m; II CH I R (jr 2-complex) (82) R (jr-allyl complex) According to this scheme, olefin isomerization occurs via a Π-σ reversible rearrangement and/or through the formation of a Π-allyl complex.

It is also assumed to be reversible, so that the observed olefin isomerization could be regarded as a side-reaction. 4) (ID The complex (IV) reacts with excess of olefin, regenerating the real catalyst (II) and forming the organosilicon compound (V). The stereochemistry of the addition to acetylenes has been studied for various types of homogeneous catalyst [63, 111, 124, 315, 992]. In practice, eis addition seems to be a common feature of hydrosilylation catalysed by transition metal complexes, although the mechanistic scheme given above does not require eis addition.

2), with the corresponding reductive elimination occurring with retention of configuration at silicon. 2. 3), where rearrangement of the Π-complex (III) to the σ-alkyl complex (IV) involves eis addition of the metal-hydrogen bond to the carbon-carbon double bond. 3. The formation of the hydrosilylated product (E) which proceeds with retention of configuration at both silicon and carbon. ) which is homogeneously catalysed by various metal complexes. The latter include Π-allyl metal complexes and carbonyl complexes which generally form σ-bonds with olefins.

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