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CH and NH bond activation in reactions of vinyl acetate, allyl cyanide, allylamine and other amines with (η‐C 5 H 5 ) 2 Rh 2 (CO)(CF 3 C 2 CF 3 )
Author(s) -
Dickson Ron S,
Jenkins Susan M
Publication year - 1990
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.590040510
Subject(s) - chemistry , allylamine , bond cleavage , medicinal chemistry , rhodium , cyanide , double bond , triple bond , ligand (biochemistry) , stereochemistry , polymer chemistry , catalysis , organic chemistry , biochemistry , polymer , receptor , polyelectrolyte
Abstract There is activation of olefinic CH bonds when (η‐C 5 H 5 ) 2 Rh 2 (CO)(CF 3 C 2 CF 3 ) 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 CH 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‐C 5 H 5 ) 2 Rh 2 {μ‐C(CF 3 )C(CF 3 )H}(μ‐CRCR′R″), and all isomers have been thoroughly characterized by NMR analysis. Similar reactions with allylamine and other amines (NH 2 R, NHMe 2 ) occur in the dark and proceed by NH bond cleavage. Near‐quantitative amounts of the products, (η‐C 5 H 5 )Rh 2 {C(CF 3 )C(CF 3 )H}(C(O)NRR′) are isolated. Spectroscopic data indicate a bridging carboxamide ligand attached to the RhRh 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.