CARBON OXYGEN BOND FORMATION ON RHODIUM CENTERS - SYNTHESIS, CHARACTERIZATION, CRYSTAL-STRUCTURE, AND REACTIONS OF TRANS-PHORH(CO)(PPH3)2

被引：25

作者：

BERNARD, KA ^{[1
]}

CHURCHILL, MR ^{[1
]}

JANIK, TS ^{[1
]}

ATWOOD, JD ^{[1
]}

机构：

[1] SUNY BUFFALO, DEPT CHEM, BUFFALO, NY 14214 USA

来源：

ORGANOMETALLICS | 1990年 / 9卷 / 01期

关键词：

D O I：

10.1021/om00115a003

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis of a rhodium phenoxide is reported. The complex trans-PhORh(CO)(PPh3)2 crystallizes in the centrosymmetric monoclinic space group P2l/c with a = 15.794 (3) Å, b = 11.449 (2) Å, c = 20.025 (3) Å, β = 100.220 (13)°, V = 3562 (1) Å3, and Z = 4. Diffraction data (Mo Kα, 2θ = 4.5-50.0°) were collected with a Syntex P21 diffractometer, and the structure was refined to RF = 2.8% for 5293 reflections. The structure is isomorphous with the iridium analogue. Important dimensions include Rh‒P = 2.337 (l)-2.357 (1) Å, Rh-CO = 1.801 (3) Å, Rh-OPh = 2.044 (2) Å, and Rh-O-C(phenoxide) = 125.52 (19)°. This complex reacts with Ph2CHC(O)Cl to give the ester Ph2CHC(O)OPh and with MeI to give anisole, PhOMe. The formation of anisole from the rhodium phenoxide is in contrast to the failure to eliminate ethers from similar iridium complexes and is consistent with the known preference for elimination from second-row (rather than third-row) transition-metal complexes. © 1990, American Chemical Society. All rights reserved.

引用

页码：12 / 16

页数：5

共 29 条

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[2]

BARKAN M, UNPUB

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