Hydrogen Shift Reactions of Rhenium Hydrido Carbyne Complexes
收藏NIAID Data Ecosystem2026-03-07 收录
下载链接：
https://figshare.com/articles/dataset/Hydrogen_Shift_Reactions_of_Rhenium_Hydrido_Carbyne_Complexes/2541706
下载链接
链接失效反馈官方服务：
资源简介：
Rhenium hydrido carbyne complexes Re(CCHC(CMe3)CCR)HCl(PMe2Ph)3 (R = H, n-pentyl) undergo 1,2-hydrogen shift reactions from the
metal to the carbyne carbon atom to give complexes Re(HCCHC(CMe3)CCR)HCl(PMe2Ph)3, which have two isomeric
forms, namely, a metallabicyclo[3.1.0]hexatriene complex, in which
the chloride is cis to the metal-bonded CH, and an alkyne–carbene
complex, in which the chloride is trans to the metal-bonded CH. In
contrast, a similar transformation does not occur for the analogous
complex Re(CCHC(CMe3)CCSiMe3)HCl(PMe2Ph)3, which has a SiMe3 group on the CC moiety. A computational study suggests
that the difference in the reactivity of the hydrido carbyne complexes
is related to steric effects in the corresponding hydride-shift products.
Formation of Re(HCCHC(CMe3)CCSiMe3)HCl(PMe2Ph)3 is not favored, mainly due to the steric interactions
of the SiMe3 group with CMe3 and one of the
phosphine ligands in the resulting metallabicyclo[3.1.0]hexatriene
complex, and of the SiMe3 group with the chloride ligand
in the resulting alkyne–carbene complex.
创建时间：
2012-03-12
