ISSN:
0268-2605
Keywords:
C—H activation
;
N—H activation
;
(η-C5H5)2Rh2(CO)(CF3C2CF3)
;
alkenyl
;
carboxamide
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/aoc.590040510
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