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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 17, Number 3
BKCSDE 17(3)
March 20, 1996 

Reduction of Alkyl Halides by Homonuclear Bridging Hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+
Yong Kwang Park*, Young Woong Kim
Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ -H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠ =28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.
269 - 274
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