947685-61-2Relevant academic research and scientific papers
P-C bond scission at the TRIPHOS ligand and C-CN bond cleavage in 2-methyl-3-butenenitrile with [Ni(COD)2]
Acosta-Ramirez, Alberto,Flores-Alamo, Marcos,Jones, William D.,Garcia, Juventino J.
, p. 1834 - 1840 (2009/02/02)
The use of catalytic amounts of [Ni(COD)2] and TRIPHOS (bis(2-diphenylphosphinoethyl)phenylphosphine) allows the isomerization of 2-methyl-3-butenenitrile (2M3BN) at 100°C, to yield Z- and E-2-methyl-2-butenenitrile (2M2BN) (57% and 31%, respectively), small amounts of 3-pentenenitrile (3PN) (5%), along with a mixture of nickel complexes, consisting of cis- and trans- [Ni2(μ-P(CH2CH 2PPh2)2)2(CN)2] (1, 2), cis- and irans-[Ni(TRIPHOS)(CN)2] (3, 4), [Ni(TRIPHOS)] (5), and [Ni2(μ-P(CH2CH2PPh2) 2)2] (6), where compounds 1-4 and 6 are the C-CN and P-C bond cleavage products, respectively. The persistent presence of benzene in the reaction mixture was confirmed by GC-MS. The use of stochiometric amounts of the reagents led to the isomerization of 2M3BN to Z- and E-2M2BN (47% and 44%, respectively) and 3PN (9%); the formation of complexes 2, 5, and 6 has been confirmed to take place, in addition to benzene and 1,3-butadiene. Complexes 1 and 3 were characterized by single-crystal X-ray determinations.
Methyl transfer from methylcobaloxime to (triphos)Ni(PPh3): Relevance to the mechanism of acetyl coenzyme a synthase
Eckert, Nathan A.,Dougherty, William G.,Yap, Glenn P. A.,Riordan, Charles G.
, p. 9286 - 9287 (2008/02/08)
The zerovalent nickel complex, (triphos)Ni(PPh3), is quantitatively alkylated by a methylcobaloxime reagent. Independent chemical synthesis confirms the nickel-containing product as the cation, [(triphos)NiMe]+. These studies provide small molecule precedent for a Ni(0) nucleophile during acetyl coenzyme A synthase (ACS) biocatalysis. That the corresponding (triphos)NiCO is not a substrate for the reaction provides a chemical-based rationale for ordered binding of methyl followed by CO. Copyright
