Advances in Organometallic Chemistry, Vol. 55 by Robert C. West, Anthony F. Hill, Mark J. Fink PDF

By Robert C. West, Anthony F. Hill, Mark J. Fink

ISBN-10: 0123739780

ISBN-13: 9780123739780

Just about all branches of chemistry and fabric technology now interface with organometallic chemistry - the examine of compounds containing carbon-metal bonds. This commonly acclaimed serial comprises authoritative studies that handle all facets of organometallic chemistry, a box which has improved drastically because the booklet of quantity 1 in 1964.* presents an authoritative, definitive evaluate addressing all elements of organometallic chemistry* necessary to researchers inside this energetic box and is a needs to for each glossy library of chemistry* prime quality study ebook inside of this swiftly constructing box

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100 VI MANGANESE, RHENIUM AND COPPER These metals, belonging to groups on either side of the main block of transition metals (Group VIIIB or 8, 9 and 10) commonly examined in hydrosilation catalysis, have only been employed very rarely to facilitate hydrosilation. Very few reports have emerged during the last 15 years on catalysts based on these metals and their use has generally been connected with special cases of hydrosilation. 101 Cutler’s group also reported hydrosilation of ketones with PhMe2SiH and Ph2SiH2 using [Mn(Y)(CO)4L] (YQCH3, C(O)CH3, Br; LQPPh3, CO) and compared activity of the phosphine–acetyl–carbonyl complex in particular with Wilkinson’s catalyst Rh(PPh3)3Cl.

ROY highly effective for the enantioselective hydrosilation of phenyl/alkyl or dialkyl ketones with Ar2SiH2 (ArQPh or 3-F-C6H4). 144 Korostylev et al. 146 Good to high yields and high to often exceptional (95 to 499%) enantioselectivity were achieved, at room temperature in CH2Cl2. Again, the Re(V) complex stands out as a high oxidation state metal catalyst that is insensitive to air and moisture exposure. 149 OMe O R O N NC O Re N O Cl Cl OPPh3 O P O P 2 O OMe R 42 2 R = 4-tBu-C6H4 43 It is apparent from the above brief excerpts from enantioselective hydrosilations of acetophenone alone, that chiral ligand selection for predictable high asymmetric induction is non-trivial.

98 For example, hydrosilation of styrene with PhSiH3 (10 mol% catalyst, THF, rt) yields b- or terminal adduct as the predominant product, and dehydrogenative silation occurs with terminal alkynes. Additionally, imines, which are not amenable to hydrosilation with Ln(III) catalysts, are readily hydrosilated by the Ln(II) compounds in good yields. Further, both types of Yb catalysts yield a silacyclopentene derivative as a secondary product from reactions of conjugated dienes with PhSiH3 (and also with Ph2SiH2 for isoprene).

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Advances in Organometallic Chemistry, Vol. 55 by Robert C. West, Anthony F. Hill, Mark J. Fink

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