SOLID-STATE CHEMISTRY OF MOLECULAR-METAL OXIDE CLUSTERS - BIS(TRIPHENYLPHOSPHINE)RHODIUM(I) CARBONYL DERIVATIVES

被引：35

作者：

SIEDLE, AR ^{[1
]}

GLEASON, WB ^{[1
]}

NEWMARK, RA ^{[1
]}

SKARJUNE, RP ^{[1
]}

LYON, PA ^{[1
]}

MARKELL, CG ^{[1
]}

HODGSON, KO ^{[1
]}

ROE, AL ^{[1
]}

机构：

[1] STANFORD UNIV,DEPT CHEM,STANFORD,CA 94305

来源：

INORGANIC CHEMISTRY | 1990年 / 29卷 / 09期

关键词：

D O I：

10.1021/ic00334a016

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Hydronium salts of the Keggin-type XM12O40molecular metal oxide cluster anions SiW12O40 4-, SiMo12O40 4-, PW12O40 3-, PMo12O40 3-, PMo12O40 4-, and PVMo11O40 4-react with [(Ph3P)3Rh(CO)][HC(SO2CF3)2] in CH3CN-C2H5OH to form [trans-(Ph3P)2Rh(CO)(CH3CN)]nXM12O40. These salts lose CH3CN on heating to provide [(Ph3P)2Rh(CO)]nXM12O40, which may also be obtained directly from [(Ph3P)3Rh(CO)] [HC(SO2CF3)2] in pure ethanol. These oxometalates have been characterized by IR, NMR, and X-ray absorption spectroscopy and are considered to contain isolated, lattice-stabilized (Ph3P)2Rh(CO)-(CH3CN)+and (Ph3P)2Rh(CO)+cations, with the latter being a three-coordinate, 14-electron Rh(I) species. The activity and selectivity of these compounds as catalysts for olefin isomerization and hydroformylation are described. Reaction of [(Ph3P)3Rh(CO)][HC(SO2CF3)2] with CH3CN produces [trans-(Ph3P)2Rh(CO)(CH3CN)][HC(SO2CF3)2], triclinic, P1, a = 10.669 (1) Å, b = 22.241 (2) Å, c = 9.257 (5) Å, α = 96.22 (2)°, β = 97.51 (2)°, γ = 7919 (1)°, Z = 2 V = 2131 Å3, R = 0.032, and Rw= 0.039. © 1990, American Chemical Society. All rights reserved.

引用

页码：1667 / 1673

页数：7

共 44 条

[1] POLYOXOANION SUPPORTED METAL-CARBONYLS - SYNTHESES OF THE [(OC)3M(NB2W4O19)]3- ANIONS (M=RHENIUM AND MANGANESE) [J].