Mechanism of endo-exo interconversion in η3-allyl Cp complexes:: A longstanding unresolved issue

被引：45
作者：
Ariafard, A [1 ]
Bi, SW [1 ]
Lin, ZY [1 ]
机构：
[1] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China
来源：
ORGANOMETALLICS | 2005年 / 24卷 / 10期
关键词：
D O I：
10.1021/om050161h
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Density functional theory studies of the d(6) allyl complexes CpM(CO)(eta(3)-C3H5) (M = Fe, Ru) and the d(4) allyl complex CpMo(CO)(2)(eta(3)-C3H5) show that the interconversion for CpMo(CO)(2)(eta(3)-C3H5) through the eta(3) -> eta(3) -> eta(3) pathway is intrinsically more favorable than the eta(3) -> eta(1) -> eta(3) pathway. However, the eta(3) transition states for CpM(CO)(eta(3)-C3H5) (M = Fe, Ru) are inaccessible, because one pair of the six metal d electrons has to occupy a d orbital having significant metal-Cp antibonding character in the transition structure.
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页码：2241 / 2244
页数：4
相关论文
共 33 条
[1]   Syntheses and dynamic NMR studies on 3-(1′-indenyl)propyl-N,N-bis(trimethylsylil)amine metal derivatives [J].
Ascenso, JR ;
Dias, AR ;
Fernandes, JA ;
Martins, AM ;
Rodrigues, SS .
INORGANICA CHIMICA ACTA, 2003, 356 :279-287
[2]   Isomerism of Cp-containing transition metal allyl complexes [J].
Bi, SW ;
Ariafard, A ;
Jia, GC ;
Lin, ZY .
ORGANOMETALLICS, 2005, 24 (04) :680-686
[3]   Syntheses and X-ray structures of complexes with (η3-allyl)Mo-units in oxygen-rich coordination spheres [J].
Borgmann, C ;
Limberg, C ;
Kaifer, E ;
Pritzkow, H ;
Zsolnai, L .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 580 (02) :214-224
[4]   Kinetics, thermodynamics, and effect of BPh3 on competitive C-C and C-H bond activation reactions in the interconversion of allyl cyanide by [Ni(dippe)] [J].
Brunkan, NM ;
Brestensky, DM ;
Jones, WD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (11) :3627-3641
[5]   Density functional theory study of Fe(CO)3(η2-C3H6), HFe(CO)3(η3-C3H5), and the iron-allyl bond energy [J].
Cedeño, DL ;
Weitz, E .
ORGANOMETALLICS, 2003, 22 (13) :2652-2659
[6]   Is the allylpalladium structure altered between solid and solutions? [J].
Clot, E ;
Eisenstein, O ;
Weng, TC ;
Penner-Hahn, J ;
Caulton, KG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (29) :9079-9084
[7]   AN IMPROVED METHOD FOR THE SYNTHESIS OF CATIONIC (ETA(5)-CYCLOPENTADIENYL) (ETA(3)-ALLYL)MO(CO)(NO) COMPLEXES - THE BENEFIT OF 1,2-DIMETHOXYETHANE AS A SOLVENT [J].
COSFORD, NDP ;
LIEBESKIND, LS .
ORGANOMETALLICS, 1994, 13 (04) :1498-1503
[8]  
CRABTREE RH, 2001, ORGANOMETALLIC CHEM, P122
[9]   A MOLECULAR-ORBITAL ANALYSIS OF THE REGIOSELECTIVITY OF NUCLEOPHILIC-ADDITION TO ETA-3-ALLYL COMPLEXES AND THE CONFORMATION OF THE ETA-3-ALLYL LIGAND IN L3(CO)2(ETA-3-C3H5)MOII COMPLEXES [J].
CURTIS, MD ;
EISENSTEIN, O .
ORGANOMETALLICS, 1984, 3 (06) :887-895
[10]   STEREOCHEMICALLY NONRIGID ORGANOMETALLIC COMPOUNDS .6. CONFIGURATIONAL EQUILIBRIA OF PI-C5H5MO(CO)2 ALLYL COMPLEXES [J].
DAVISON, A ;
RODE, WC .
INORGANIC CHEMISTRY, 1967, 6 (11) :2124-&
1234