SYNTHESIS OF (ETA(6)-C13H10)MN(CO)2LPF6 AND (ETA(6)-C13H9)MN(CO)2L COMPLEXES (L = PHOSPHINES AND PHOSPHITES) AND KINETIC-STUDIES OF ETA(6) TO ETA(5) RING SLIPPAGE REACTIONS

被引：11

作者：

BIAGIONI, RN

LUNA, AD

MURPHY, JL

机构：

[1] Department of Chemistry, Southwest Missouri State University, Springfield

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1994年 / 476卷 / 02期

关键词：

MANGANESE; RING SLIPPAGE; KINETIC STUDIES; PHOSPHINES; PHOSPHITES;

D O I：

10.1016/0022-328X(94)87080-2

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

This report describes the syntheses and characterizations of (eta6-C13H10)Mn(CO)2LPF6 and (eta6-C13H9)Mn(CO)2L complexes (L = P(OEt)3, PPh3, PEt3, and eta1-(diphos) (diphos = 1,2-bis(diphenylphosphino)ethane), and kinetic studies of (eta6-C13H9)Mn(CO)2L-->(eta5-C13H9)Mn(CO)2L ring slippage reactions. DELTAH(double dagger) values for the eta6-->eta5 slippage reactions of the P(OEt)3 (26.4 kCal/mol), PPh3 (23.1 kcal mol-1), and PEt3 (25.6 kcal mol-1) complexes are similar to values previously reported for CO and P(n-Bu)3 complexes. Tle unusually low value of DELTAH(double dagger) = 19.9 kcal/mol for the eta1-diphos complex is attributed to an intermediate stabilized by an intramolecular nucleophilic attack of the free end of the diphos ligand on the metal center.

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页码：183 / 188

页数：6

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