동종이핵착물인 M+(h5-MeCp)Mn(CO)2Mn(CO)5-(M+=Na+, PPN+) 와 염화알릴간의 반응에 대한 반응속도론적 연구

초록

The homobimetallic anion, M+(η5-MeCp)Mn(CO)2Mn(CO)5(M+=Na+, PPN+) was disrupted byCH2CHCH2Cl in THF at various temperatures (20oC~50oC) under the pseudo 1st order reaction conditions where excessof allyl chloride was employed under a nitrogen atmosphere. This homobimetallic anion seems to be involved in a con-certed reaction mechanism in which a four-centered transition state is proposed. After undergoing the transition state, thisreaction eventually leads to (MeCp)Mn(CO)3 on addition of CO and ( 1-alyl)Mn(CO)5, respectively. However, in caseof Na+ analog, Na+ may play a novel counter ion effect on the disruption reaction either by transfering one terminal COfrom the Mn(CO)5 moiety on to the ( 5-MeCp)Mn(CO)2 of the coresponding homobimetallic complex, eventuallyresulting in ( 5-MeCp)Mn(CO)3 or through the interaction between Na+ and the leaving group (Cl) of allyl chloride. Thisreaction is of overall second order with respect to homobimetallic complex with the activation parameters ( H=17.150.17 kcal/mol, S= 9.630.10 e.u. for Na+ analog; H=22.130.21 kcal/mol, S=9.740.19 e.u. for PPN+analog reaction).

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