Facile C–N bond cleavage mediated by electron-rich cyclopentadienyl cobalt(I) complexes
作者:Helmut Werner、Gerhard Hörlin、William D Jones
DOI:10.1016/s0022-328x(98)00362-3
日期:1998.7
does not react by N–C bond cleavage. The conversion of 2 to 4 in C6D6, acteone-d6 and methanol-d4 follows first order kinetics with a rate that is almost independent of the concentration of free PMe3. Both 2 and 6 react with Ph2CN2 to give the C,C-bound ketenimine complexes [C5H5Co(κ2-C,C-Ph2CCNR)(PMe3)] (9, 10) of which that with R=Tol rearrangesthermally to the more stable N,C-bound isomer 11.
[C 5 H 5 Co(PMe 3)2 ](1)与一当量的CNCH 2 Ph反应导致形成取代产物[C 5 H 5 Co(CNCH 2 Ph)(PMe 3)](2),其即使在室温下也经历分子内氧化加成而得到异构体[C 5 H 5 Co(CN)(CH 2 Ph)(PMe 3)](4)。相应的Cp * Co衍生物[C 5 Me 5 Co(CN)(CH 2 Ph)(PMe 3)](8)从[C 5 Me 5 Co(PMe 3)2 ](5)和CNCH 2 Ph中获得。与2相反,类似化合物[C 5 H 5 Co(CNTol)(PMe 3)] (6)是非常惰性的,不会因N–C键断裂而发生反应。在C 6 D 6,Acteone-d 6和甲醇-d 4中2到4的转化遵循一级动力学,其速率几乎与游离PMe 3的浓度无关。两个都2和6的Ph反应2 CN 2,得到Ç,Ç结合的烯酮亚胺络合物[C 5 H ^ 5的Co(κ
Cp*Co(IPr): synthesis and reactivity of an unsaturated Co(<scp>i</scp>) complex
作者:John M. Andjaba、Jesse W. Tye、Pony Yu、Iraklis Pappas、Christopher A. Bradley
DOI:10.1039/c5cc06756a
日期:——
Coordinatively unsaturated Cp*Co(IPr) (2) has been isolated and displays reactivity consistent with a Cp*CoL fragment, undergoing ligand addition/NHC displacement and oxidative addition of dihydrogen.
C−C Activation in Biphenylene. Synthesis, Structure, and Reactivity of (C<sub>5</sub>Me<sub>5</sub>)<sub>2</sub>M<sub>2</sub>(2,2‘-biphenyl) (M = Rh, Co)
作者:Christophe Perthuisot、Brian L. Edelbach、Deanna L. Zubris、William D. Jones
DOI:10.1021/om961059a
日期:1997.5.1
rhodium and cobaltcomplexes, respectively. (C5Me5)2Rh2(2,2‘-biphenyl) reacted with CO to give (C5Me5)Rh(CO)2 and (C5Me5)Rh(CO)(2,2‘-biphenyl), while the cobalt analog gave (C5Me5)Co(CO)2 and fluorenone. (C5Me5)2Co2(2,2‘-biphenyl) gave (C5Me5)Co(PMe3)2 and (C5Me5)Co(PMe3)(2,2‘-biphenyl) when reacted with PMe3, as determined by X-ray crystallography of the latter complex. Both complexes were found to
用(C 5 Me 5)M(C 2 H 4)2(M = Rh,Co)实现联苯的碳-碳键裂解,得到双金属物质(C 5 Me 5)2 M 2(2,2' -联苯)。这些复合物的同晶型固态X射线结构显示联苯基板是σ配位到一种金属和η 4结合的另一个。这些复合物显示出动态行为,交换了σ键和π键。对两种双核物质以及这两种物质相互转化的能垒进行了可变温度NMR研究(C 5 Me 5)片段计算为Δ G ^ ⧧(350 K)= 16.8千卡/摩尔和Δ ģ ⧧(248 K)分别11.4千卡/摩尔的铑和钴络合物,=。(C 5 Me 5)2 Rh 2(2,2'-联苯)与CO反应生成(C 5 Me 5)Rh(CO)2和(C 5 Me 5)Rh(CO)(2,2'-联苯),而钴类似物则提供(C 5 Me 5)Co(CO)2和芴酮。得到(C 5 Me 5)2 Co 2(2,2'-联苯)(C 5Me 5)Co(PMe 3)2和(C