Preparation of stable alkyl complexes of Ni(I) and their one-electron oxidation to Ni(II) complex cations

被引：99
|
作者：
Kitiachvili, KD [1 ]
Mindiola, DJ [1 ]
Hillhouse, GL [1 ]
机构：
[1] Univ Chicago, Searle Chem Lab, Dept Chem, Chicago, IL 60637 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2004年 / 126卷 / 34期
关键词：
D O I：
10.1021/ja047052z
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The three-coordinate nickel(I) alkyl complexes (dtbpe)Ni(CH2CMe3) (2), (dtbpe)Ni(CH2SiMe3) (3), and (dtbpe)Ni(CH2CMe2Ph) (4) have been prepared by treatment of [(dtbpe)NiCl]2 with alkyllithium reagents. While thermally robust, they each undergo mild one-electron oxidation to give the corresponding Ni(II) complex cations [(dtbpe)Ni(CH2CMe3)+] (5), [(dtbpe)Ni(CH2SiMe3)+] (6), and [(dtbpe)Ni(CH2CMe2Ph)+] (7) as red-brown [PF6-] or [BArF4-] salts. In contrast to cationic amido and phosphido analogues that undergo α-deprotonation to afford imido and phosphinidene derivatives, deprotonation of 5-7 occurs at a γ-CH3 group to give metallacyclobutane products (dtbpe)Ni(CH2CMe2CH2) (8), (dtbpe)Ni(CH2SiMe2CH2) (9), and (dtbpe)Ni(CH2CPhMeCH2) (10), not (dtbpe)Ni=CHR. Copyright © 2004 American Chemical Society.
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收藏
页码：10554 / 10555
页数：2
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