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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 17, Number 2
BKCSDE 17(2)
February 20, 1996 

Kinetics and Mechanism of Substitution Reaction of PPN+(η5-MeCp)Mn(CO)2Cl- with PR3 (R=Me, Et, OEt, C6H5
Yong Kwang Park*, Yong Gu Lee, Gyu Shik Kim
The transition metal carbonylate, PPN+(η 5-MeCp)Mn(CO)2Cl- undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, C6H5 in THF at elevated temperatures (40 ℃ up to 60 ℃) under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(η 5-MeCp)Mn(CO)2Cl-]; however, the negative entropy changes of activation (ΔS≠=-19.3 e.u. for P(OEt)3; ΔS≠=-16.4 e.u. for PPh3) suggest the existence of the intermediate, ((η 3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (η 5-MeCp)Mn(CO)2(PR3).
138 - 142
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