Synthesis, Structure, and Reactivity of Group VI Metal Complexes Bearing Group IV Metallocenyldiphosphine Moieties and a Pentamethylcyclo pentadienyl Ligand
Synthesis, Structure, and Reactivity of Group VI Metal Complexes Bearing Group IV Metallocenyldiphosphine Moieties and a Pentamethylcyclo pentadienyl Ligand
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带有 IV 族金属茂基二膦部分和五甲基环戊二烯基配体的 VI 族金属配合物的合成、结构和反应性
DOI：
10.1021/om400088d
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发表时间：
2013
期刊：
影响因子：
2.8
通讯作者：
Yoshiaki Nishibayashi
中科院分区：
文献类型：
--
作者：
Takamasa Miyazaki;Yoshiaki Tanabe;Masahiro Yuki;Yoshihiro Miyake;Yoshiaki Nishibayashi
合成了一系列含有IV族烯基双膦和五甲基双膦配体的VI族金属配合物，并对其结构进行了表征。三核配合物与KC_（8-）反应得到相应的中性氯桥配合物。进一步与NaBArF 4反应得到相应的单阳离子氯桥配合物。另一方面，中性氯桥络合物与n-BuLi的反应得到相应的氯桥烷基络合物，其中第IV族茂金属（III）部分和配位不饱和的第VI族金属（II）中心非常接近。光谱学和晶体学研究的氯桥烷基络合物与CO或质子酸的反应表明，进一步prachionation发生在烷基zirconocene（III）部分。
A series of group VI metal complexes bearing a group IV metallocenyldiphosphine moiety and a pentamethylcyclopentadienyl ligand have been prepared and structurally characterized. Reactions of trinuclear complexes with KC8give the corresponding neutral chloride-bridged complexes. Further reaction of the resulting chloride-bridged complex with NaBArF4gives the corresponding monocationic chloride-bridged complex. On the other hand, reactions of the neutral chloride-bridged complexes withn-BuLi give the corresponding chloride-bridged alkyl complexes, where the group IV metallocene(III) moiety and the coordinatively unsaturated group VI metal(II) center are in close proximity. Spectroscopic and crystallographic studies of the reaction of a chloride-bridged alkyl complex with CO or a protic acid indicate that further disproportionation takes place at the alkyl zirconocene(III) moiety.