Experimental and Computational Study of Auxiliary Molecular Effects on the Mechanism of the Addition of Hydrazines to a Low-Valent Germanium Complex

被引：29
作者：
Brown, Zachary D. [1 ]
Guo, Jing-Dong [2 ]
Nagase, Shigeru [2 ]
Power, Philip P. [1 ]
机构：
[1] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
[2] Inst Mol Sci, Dept Theoret & Computat Mol Sci, Okazaki, Aichi 4448585, Japan
来源：
ORGANOMETALLICS | 2012年 / 31卷 / 09期
关键词：
FRUSTRATED LEWIS PAIRS; FREE HYDROGEN ACTIVATION; METAL-FREE; CARBON-DIOXIDE; H BOND; AMMONIA; CAGE; P-4; INSERTION; COMPOUND;
D O I：
10.1021/om300271c
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Reaction of the diarylgermylene Ge(Ar-Me6)(2) (Ar-Me6 = C6H3-2,6-(C6H2-2,4,6-(CH3)(3))(2)) with hydrazine and methylhydrazine gave the first structurally characterized Ge(IV) hydrazide complexes, (Ar-Me6)(2)Ge(H)NHNHR (R = H, Me). A detailed computational study of, the mechanism of this N-H bond activation showed that the reaction proceeds via an intermolecular proton transfer, which is mediated by a second equivalent of hydrazine that interacts with the hydrazine. Ge(Ar-Me6)(2) adduct intermediate through N- - -H hydrogen bonding. This auxiliary effect is blocked when the substituted derivative N,N-dimethylhydrazine is used, and a Lewis adduct complex of Ge(Ar-Me6)(2) is the only product obtained.
引用
收藏
页码：3768 / 3772
页数：5
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