113158-84-2Relevant academic research and scientific papers
The reactions of alkyltrimethylphosphinenickel complexes with isocyanides and alkynes
Bochmann, Manfred,Hawkins, Ian,Sloan, Martin P.
, p. 371 - 378 (1987)
t-Butylisocyanide reacts with NiRCl(PMe3)2 (R=CH3, Ia; R=CH2SiMe3, Ib) to give, successively, the products of mono- and di-insertion into the nickel-carbon bonds; with more than two equivalents of isocyanide, trimethylphosphine ligands are displaced.In contrast to related palladium reactions, cyclohexyl isocyanide gives mono-insertion products only, while benzyl isocyanide is polymerised.The reactions of diphenylacetylene with Ia and Ib in methanol give (Z)-vinylnickel complexes, trans-NiCl(PMe3)2, while from reaction in diethyl ether a precursor complex can be isolated.On heating the (Z)-vinyl complexes come into thermodynamic equilibrium with their (E)-isomers.The vinyl complexes are stereochemically rigid and resistant to further insertion.
Insertion of Alkynes into Organonickel Functions as a Synthesis of Vinylnickel Compounds
Klein, Hans-Friedrich,Reitzel, Lutz
, p. 1115 - 1118 (2007/10/02)
The diamagnetic vinylnickel compounds trans-Ni(CR1=CR2R3)Cl(PMe3)2 (1a: R1 = R2 = C6H5, R3 = CH3; 2a: R1= C6H5, R2 = R3 = CH3; 3a: R1 = R2 = CH3, R3 = C6H5; 4a: R1 = R2 = R3 = C6H5) and Ni(CR1=CR2R3)(acac)(PMe3) (5: R1 = R2 = C6H5, R3 = CH3) are formed by insertion of diphenylethyne and 1-phenylpropyne into methyl- or phenylnickel moieties as Z isomers, that are thermally equilibrated with their E isomers. 1-Phenylethyne and 1-phenylpropyne selectively produce (1-phenylvinyl)nickel compounds.Exchange of halide gives bromides 1b, 2b, 4b and iodides 1c, 2c, 4c, and a cyanide 1d.Action of LiR (R = Me, CCCMe3) on 1a followed by reductive elimination yields olefins RR1C=CR2R3 while mineral acids or iodine cleave the Ni-C bonds of 1a to give the corresponding olefins (R = H, I).A high-yield synthesis of chloro(phenyl)bis(trimethylphosphane)nickel is also described.
