P−C Bond Scission at the TRIPHOS Ligand and C−CN Bond Cleavage in 2-Methyl-3-butenenitrile with [Ni(COD)2]
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- 作者：Alberto Acosta-Ramí ; rez ; Marcos Flores-Á ; lamo ; William D. Jones ; Juventino J. Garcí ; a
- 刊名：Organometallics
- 出版年：2008
- 出版时间：April 28, 2008
- 年：2008
- 卷：27
- 期：8
- 页码：1834 - 1840
- 全文大小：175K
- 年卷期：v.27,no.8(April 28, 2008)
- ISSN：1520-6041
文摘
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(CH2CH2PPh2)2)2(CN)2] (1, 2), cis- and trans-[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.