Manganese- and Rhodium-Catalyzed Phenylsilane Hydrosilation−Deoxygenation of Iron Acyl Complexes Cp(L)(CO)FeC(O)R (L = CO, PPh<sub>3</sub>, P(OMe)<sub>3</sub>, P(OPh)<sub>3</sub>; R = CH<sub>3</sub>, Ph, CHMe<sub>2</sub>, CMe<sub>3</sub>)
作者:Zhibiao Mao、Brian T. Gregg、Alan R. Cutler
DOI:10.1021/om970659m
日期:1998.5.1
The manganese carbonyl acyl complexes L(CO)4MnC(O)R (L = CO, R = CH3 (2a); L = CO, R = Ph (2b); L = PPh3, R = CH3 (2c)) are precatalysts for the PhSiH3 hydrosilation−deoxygenation of Cp(CO)2FeC(O)CH3 (1a) to Cp(CO)2FeCH2CH3 (6a). Thus, 2a (4%) and 1.1 equiv of PhSiH3 reduce 1a initially to a mixture of [Cp(CO)2FeCH(CH3)O]3-xHxSiPh (x = 2 (3b), 1 (4b), and 0 (5b)) (7−8 h), which transforms to a mixture
羰基锰锰配合物L(CO)4 MnC(O)R(L = CO,R = CH 3(2a); L = CO,R = Ph(2b); L = PPh 3,R = CH 3(2c))是用于Cp(CO)2 FeC(O)CH 3(1a)到Cp(CO)2 FeCH 2 CH 3(6a)的PhSiH 3硅氢化-脱氧的预催化剂。因此,2a(4%)和1.1当量的PhSiH 3最初将1a还原为[Cp(CO)2 FeCH(CH 3)O]的混合物3 - x H x SiPh(x = 2(3b),1(4b)和0(5b))(7-8 h),转换为5b(62%)和6a(35%)的混合物( 12小时)。同样,2b和PhSiH 3将1a转换为包含4%3b,22%4b,72%5b和2%6a(30分钟),然后达到15-20%6a(12 h)的混合物。使用2c作为预催化剂可以选择性地产生71%的4b和10%的6a(30分钟),然后高达1
Methyl and phenyl rearrangements in acyclic Fe II alkylidenes
作者:Robert S. Bly、Ruta K. Bly
DOI:10.1039/c39860001046
日期:——
Dicarbonyl(η5-cyclopentadienyl)-(2,2-dimethylpropylidene)iron(II) and -(2-methyl-2-phenylpropylidene)iron(II) tetrafluoroborates, (6) and (10), prepared by protonation of the analogous FeIIα-ethoxyalkyls, rearrange to dicarbonyl(η5-cyclopentadienyl)-(η2-2-methylbut-2-ene)iron(II) and -(η2-2-methyl-1-phenylprop-1-ene)iron(II) tetrafluoroborates, (7) and (11), by shift of a methyl and phenyl group, respectively