Synthesis and chemistry of secondary alkyl iodide complexes of the formula[(η5-C5H5)Re(NO)(PPh3)(ICHRR′)]+BF4−
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Reactions of deuterodichloromethane complex [(η5-C5H5)Re(NO)(PPh3) (ClCD2Cl)]+BF4- with (a) isopropyl iodide, (b) sec-butyl iodide, (c) cyclopentyl iodide, and (d) cyclohexyl iodide give secondary alkyl iodide complexes [(η5-C5H5)Re(NO) (PPh3)(ICHRR′)]+BF4- (3a-d) in good to high NMR yields, depending upon the quantity of alkyl iodide employed. These compounds are much less stable than analogous primary alkyl iodide complexes, but analytically pure 3d can be isolated from the reaction of (η5-C5H5)Re(NO)(PPh3)(CH3) and HBF4·OEt2 in neat cyclohexyl iodide (73%). Complex 3d decomposes in CD2Cl2 to give cyclohexyl fluoride, cyclohexene (74% total) and bridging halide complexes [(η5-C5H5)Re(NO)(PPh3)]2X+BF4- (X = I, 33%; Cl, 36%). The formation of cyclohexyl fluoride suggests BF4- participation in carbon-iodine bond cleavage. Reaction of 3d and PPh3 gives the substitution product [Ph3PC6H11]+BF4- (24%), cyclohexyl fluoride (24%), cyclohexene (30%) and (η5-C5H5)Re(NO)(PPh3)(I) (7, 95%). An analogous reaction of 3d and PPN+Br- gives cyclohexene (57%) and 7 (99%). © 1991.
author list (cited authors)
Igau, A., & Gladysz, J. A.