MOLECULAR SOLID-STATE ORGANOMETALLIC CHEMISTRY OF TRIPODAL (POLYPHOSPHINE)METAL COMPLEXES - CATALYTIC-HYDROGENATION OF ETHYLENE AT IRIDIUM

被引：66

作者：

BIANCHINI, C ^{[1
]}

FARNETTI, E ^{[1
]}

GRAZIANI, M ^{[1
]}

KASPAR, J ^{[1
]}

VIZZA, F ^{[1
]}

机构：

[1] UNIV TRIESTE,DIPARTIMENTO SCI CHIM,I-34127 TRIESTE,ITALY

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1993年 / 115卷 / 05期

关键词：

D O I：

10.1021/ja00058a021

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The solid-gas reactions of [(triphos)Ir(H)2(C2H4)]BPh4 (1) with CO, C2H4, and H-2 are described [triphos = MeC(CH2PPh2)3]. The gaseous reactants promote the elimination of ethane from 1 and the formation of [(triphos)Ir(CO)2]BPh4, [(triphos)Ir(C2H4)2]BPh4, and [(triphos)Ir(H)2]BPh4, respectively. The latter 16-electron species is isolable in the solid state at temperatures <70-degrees-C. At higher temperatures, [(triphos)Ir(H)2]+ dimerizes in the solid state to give the tetrahydride [(triphos)HIr(mu-H)2HIr(triphos)]2+. Dimerization is avoided when the unsaturated fragment is incorporated into the lattice of a polyoxometalate cluster such as PW12O403-. The complex [(triphos)Ir(H)2(C2H4)]BPh4 is an effective catalyst for the hydrogenation of ethylene in the solid state at 60-degrees-C. Comparisons are made with analogous fluid solution-phase systems.

引用

页码：1753 / 1759

页数：7

共 32 条

[1] ASSEMBLING ETHYLENE, ALKYL, HYDRIDE, AND CO LIGANDS AT IRIDIUM
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[2] HYDROGEN-TRANSFER REACTIONS OF THE TRIHYDRIDE [(MEC(CH2PPH2)3)RHH3] - A SIMPLE ROUTE TO RHODIUM CIS HYDRIDE ETA-2-ALKENE COMPLEXES
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[4] STEPWISE METAL-ASSISTED REDUCTION OF ETA-4-COORDINATED BENZENE TO CYCLOHEXENE
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[7] SYNTHESIS, CHARACTERIZATION, AND ELECTROCHEMICAL PROPERTIES OF A FAMILY OF DINUCLEAR RHODIUM COMPLEXES CONTAINING 2 TERMINAL HYDRIDE LIGANDS AND 2 HYDRIDE (OR CHLORIDE) BRIDGES - STOICHIOMETRIC AND CATALYTIC-HYDROGENATION REACTIONS OF ALKYNES AND ALKENES
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[8] SOLID-STATE ORGANOMETALLIC CHEMISTRY OF TRIPODAL (POLYPHOSPHINE)METAL COMPLEXES - C-H ACTIVATION REACTIONS AT COBALT(I) ENCAPSULATED INTO THE TETRAPHOSPHINE P(CH2CH2PPH2)3
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[9] TRIPODAL POLYPHOSPHINE LIGANDS IN HOMOGENEOUS CATALYSIS .1. HYDROGENATION AND HYDROFORMYLATION OF ALKYNES AND ALKENES ASSISTED BY ORGANORHODIUM COMPLEXES WITH MEC(CH2PPH2)3
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[10] AN ETA-4-BENZENE SPECIES MEDIATES ACETYLENE CYCLOTRIMERIZATION
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