Activation of sp3 Carbon−Hydrogen Bonds by Cobalt and Iron Complexes and Subsequent C−C Bond Formation

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• 作者：Guoqiang Xu ; Hongjian Sun ; Xiaoyan Li
• 刊名：Organometallics
• 出版年：2009
• 出版时间：October 26, 2009
• 年：2009
• 卷：28
• 期：20
• 页码：6090-6095
• 全文大小：830K
• 年卷期：v.28,no.20(October 26, 2009)
• ISSN：1520-6041

文摘

The sp³ C−H bond activation induced by CoMe(PMe₃)₄ and FeMe₂(PMe₃)₄ was investigated. C(sp³)-cyclometalated complexes, based on diphosphinito PCP ligand (Ph₂POCH₂)₂CH₂, Co{(Ph₂POCH₂)₂CH}(PMe₃)₂ (1), and Fe{(Ph₂POCH₂)₂MeC}(H)(PMe₃)₂ (2), were obtained under mild conditions. Iodomethane is oxidatively added to 1, affording Co{(Ph₂POCH₂)₂CH}(PMe₃)(Me)(I) (3). Monocarbonylation of the hydrido-iron complex 2 occurs with substitution of a trimethylphosphine ligand trans to the hydrido ligand, affording Fe{(Ph₂POCH₂)₂MeC}(H)(CO)(PMe₃) (4). The reaction of 2 with phenylacetylene delivered the demetalated new diphosphine ligand (Ph₂POCH₂)₂CHCH₃ (6) and bis(phenylethinyl)iron complex Fe(PhCC)₂(PMe₃)₄ (5). The new complexes 1−4 were characterized by spectroscopic methods and by X-ray diffraction analysis.