RING MIGRATION REACTIONS OF (C5ME5)RH(PME3)H2 - EVIDENCE FOR ETA-3 SLIPPAGE AND METAL-TO-RING HYDRIDE MIGRATION

被引：48

作者：

JONES, WD

KUYKENDALL, VL

SELMECZY, AD

机构：

[1] Department of Chemistry, University of Rochester, Rochester

来源：

ORGANOMETALLICS | 1991年 / 10卷 / 05期

关键词：

D O I：

10.1021/om00051a057

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactions of (C5Me5)Rh(PR3)H2(PR3 = PMe3, PMe2Ph, PMePh2, PPh3) with D2 gas occur quickly at 25-degrees-C, leading to the stepwise exchange of hydrogen for deuterium. Kinetic studies indicate a second-order reaction mechanism involving rhodium and deuterium. (C5Me5)Rh(PMe3)H2 also reacts with PMe3 at 40 degrees-C to give C5Me5H and HRh(PMe3)4, a reaction that also displays biomecular kinetics. Isotope effect studies show no rate difference with the dideuteride rhodium complex. The mechanism(s) of these reactions are discussed in light of the kinetic requirements. The reactions of (C5Me5)Rh(PR3)(Ph)H with H2 have also been studied and found to lead to (C5Me)Rh(PR3)H2.

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页码：1577 / 1586

页数：10

相关论文

共 42 条

[1] PHOTOCHEMICAL SUBSTITUTION OF ETHENE AND H/D EXCHANGE IN (ETA-5-CYCLOPENTADIENYL)BIS(ETHENE)RHODIUM [J].

BELT, ST ;

DUCKETT, SB ;

HADDLETON, DM ;

PERUTZ, RN .

ORGANOMETALLICS, 1989, 8 (03) :748-759

[2] ALKYL, ALKYNYL, AND OLEFIN COMPLEXES OF "BIS(PI-CYCLOPENTADIENYL)-MOLYBDENUM OR BIS(PI-CYCLOPENTADIENYL)-MOLYB-TUNGSTEN - REVERSIBLE METAL-TO-RING TRANSFER OF AN ETHYL GROUP [J].

BENFIELD, FW ;

GREEN, MLH .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1974, (12) :1324-1331

[3]

BERGMAN RG, 1983, J AM CHEM SOC, V105, P3929

[4] PHOTOACTIVATION OF ALKANES BY CARBONYL(ETA-5-CYCLOPENTADIENYL)DIHYDRIDOIRIDIUM - SOLUTION AND MATRIX-ISOLATION STUDIES [J].

BLOYCE, PE ;

REST, AJ ;

WHITWELL, I ;

GRAHAM, WAG ;

HOLMESSMITH, R .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (13) :846-848

[5]

BUCHANAN JM, 1985, J AM CHEM SOC, V107, P1537

[6] REACTIVITY OF ETA-5-INDENYLRHODIUM(I) COMPLEXES - CYCLOCOTRIMERIZATION OF ALKYNES WITH ALKENES [J].

CADDY, P ;

GREEN, M ;

OBRIEN, E ;

SMART, LE ;

WOODWARD, P .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1977, 16 (09) :648-649

[7] INTERMEDIATES IN ASSOCIATIVE PHOSPHINE SUBSTITUTION-REACTIONS OF (N5-C5H5)W(CO)2(NO) [J].

CASEY, CP ;

JONES, WD ;

HARSY, SG .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1981, 206 (03) :C38-C42

[8] CONVERSION OF AN ETA-5-CYCLOPENTADIENYL-METAL COMPLEX TO AN ETA-1-CYCLOPENTADIENYL-METAL COMPLEX UPON ADDITION OF TRIMETHYLPHOSPHINE [J].

CASEY, CP ;

JONES, WD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (19) :6154-6156

[9] INTERMEDIATES IN THE ASSOCIATIVE PHOSPHINE SUBSTITUTION-REACTION OF (ETA-5-C5H5)RE(CO)3 [J].

CASEY, CP ;

OCONNOR, JM ;

JONES, WD ;

HALLER, KJ .

ORGANOMETALLICS, 1983, 2 (04) :535-538

[10] INTERCONVERSION OF ETA-5-C5H5, ETA-1-C5H5, AND IONIC ETA-0-C5H5 RHENIUM COMPOUNDS - X-RAY CRYSTAL-STRUCTURE OF [RE(NO)(CH3)(PME3)4]+[C5H5]- [J].

CASEY, CP ;

OCONNOR, JM ;

HALLER, KJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (05) :1241-1246

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