C-H AND N-H BOND ACTIVATION IN REACTIONS OF VINYL-ACETATE, ALLYL CYANIDE, ALLYLAMINE AND OTHER AMINES WITH (ETA-C5H5)2RH2(CO)(CF3C2CF3)

被引：3
|
作者：
DICKSON, RS
JENKINS, SM
机构：
[1] Department of Chemistry, Monash University, Clayton, Victoria
来源：
APPLIED ORGANOMETALLIC CHEMISTRY | 1990年 / 4卷 / 05期
关键词：
(η‐C[!sub]5[!/sub]H[!sub]5[!/sub])[!sub]2[!/sub]Rh[!sub]2[!/sub](CO)(CF[!sub]3[!/sub]C[!sub]2[!/sub]CF[!sub]3[!/sub]); alkenyl; carboxamide; CH activation; NH activation;
D O I：
10.1002/aoc.590040510
中图分类号：
O69 [应用化学];
学科分类号：
081704 ;
摘要：
There is activation of olefinic CH bonds when (η‐C5H5)2Rh2(CO)(CF3C2CF3) is treated with vinyl acetate or allyl cyanide. These reactions are initiated by exposure to sunlight. In the vinyl acetate reaction, each of the three vinylic CH bonds can be broken, but there is strong preference for cleavage at the substituted carbon. The products formed in these reactions are bisalkenyl complexes of the type (η‐C5H5)2Rh2{μ‐C(CF3)C(CF3)H}(μ‐CRCR′R″), and all isomers have been thoroughly characterized by NMR analysis. Similar reactions with allylamine and other amines (NH2R, NHMe2) occur in the dark and proceed by NH bond cleavage. Near‐quantitative amounts of the products, (η‐C5H5)Rh2{C(CF3)C(CF3)H}(C(O)NRR′) are isolated. Spectroscopic data indicate a bridging carboxamide ligand attached to the RhRh bond from oxygen and nitrogen donor sites. It is proposed that coordination of O or N to rhodium has a strong influence on all of the reactions studied. Copyright © 1990 John Wiley & Sons Ltd.
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页码：493 / 501
页数：9
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