Chemistry of tetrakis(triethyl phosphite) nickel hydride, HNi[P(OEt)3]4+. II. Reaction with 1,3-butadiene. Catalytic formation of hexadienes
01 Nov 1970-Journal of the American Chemical Society (American Chemical Society)-Vol. 92, Iss: 23, pp 6777-6784
About: This article is published in Journal of the American Chemical Society.The article was published on 1970-11-01. It has received 85 citations till now. The article focuses on the topics: Nickel hydride & Catalysis.
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TL;DR: In this article, the preparation of catalysts for cationic nickel and palladium complexes with multidentate ligands has been studied and a review of the recent advances is presented.
302 citations
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TL;DR: Nickel PCP-pincer hydride complexes catalyze chemoselective hydrosilylation of C═O bonds of aldehydes and ketones in the presence of other functional groups as discussed by the authors.
215 citations
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TL;DR: This review begins with the significance and a very brief history of nickel hydride complexes, followed by various methods and spectroscopic or crystallographic tools used to synthesize and characterize these complexes.
Abstract: Nickel hydride complexes, defined herein as any molecules bearing a nickel hydrogen bond, are crucial intermediates in numerous nickel-catalyzed reactions. Some of them are also synthetic models of nickel-containing enzymes such as [NiFe]-hydrogenase. The overall objective of this review is to provide a comprehensive overview of this specific type of hydride complexes, which has been studied extensively in recent years. This review begins with the significance and a very brief history of nickel hydride complexes, followed by various methods and spectroscopic or crystallographic tools used to synthesize and characterize these complexes. Also discussed are stoichiometric reactions involving nickel hydride complexes and how some of these reactions are developed into catalytic processes.
211 citations
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TL;DR: This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Brϕnsted acid and Pd(0) complex.
Abstract: A facile, highly stereo- and regioselective hydrometalation of alkynes generating alkenylmetal complex is disclosed for the first time from a reaction of alkyne, carboxylic acid, and a zerovalent group 10 transition metal complex M(PEt3)4 (M = Ni, Pd, Pt). A mechanistic study showed that the hydrometalation does not proceed via the reaction of alkyne with a hydridometal generated by the protonation of a carboxylic acid with Pt(PEt3)4, but proceeds via a reaction of an alkyne coordinate metal complex with the acid. This finding clarifies the long proposed reaction mechanism that operates via the generation of an alkenylpalladium intermediate and subsequent transformation of this complex in a variety of reactions catalyzed by a combination of Brϕnsted acid and Pd(0) complex. This finding also leads to the disclosure of an unprecedented reduction of alkynes with formic acid that can selectively produce cis-, trans-alkenes and alkanes by slightly tuning the conditions.
185 citations
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TL;DR: In sharp contrast to the corresponding Ni(II)-catalyzed hydrovinylation, 1-aryl-substituted 1,3-dienes give almost exclusively achiral linear 1,4-addition products, unless the 2-position is also substituted.
Abstract: Monosubstituted acyclic (E)-1,3-dienes undergo efficient hydrovinylation giving (Z)-3-alkylhexa-1,4-dienes upon treatment with catalytic amounts of bidentate phosphine-CoCl2 complexes {[P∼P](CoCl2)} and Me3Al in an atmosphere of ethylene. The regioselectivity of the reaction (i.e., 1,4- or 1,2-addition) depends on the nature of the ligand and temperature at which the reaction is carried out. Complexes derived from (RR)-DIOP and (SS)-BDDP at −45 °C give very high enantioselectivities for several prototypical 1,3-dienes. In sharp contrast to the corresponding Ni(II)-catalyzed hydrovinylation, 1-aryl-substituted 1,3-dienes give almost exclusively achiral linear 1,4-addition products, unless the 2-position is also substituted. Solid-state structures of the precatalysts are presented.
111 citations