Synthesis, separation, and stereochemical studies of chiral-at-metal rhodium(III) complexes. Crystal structure of (S-Rh,R(C))-[(eta(5)-C(5)Me(5))RhCl{Ph(2)PCH(Me)CH(2)PPh(2)}]BF4

被引：33

作者：

Carmona, D ^{[1
]}

Lahoz, FJ ^{[1
]}

Oro, LA ^{[1
]}

Lamata, MP ^{[1
]}

Viguri, F ^{[1
]}

SanJose, E ^{[1
]}

机构：

[1] UNIV ZARAGOZA,INST CIENCIA MAT ARAGON,ESCUELA UNIV INGEN TECN & IND,DEPT QUIM INORGAN,E-50009 ZARAGOZA,SPAIN

来源：

ORGANOMETALLICS | 1996年 / 15卷 / 13期

关键词：

D O I：

10.1021/om960134e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis of chiral-at-metal [(eta(5)-C(5)Me(5))RhX(prophos)]X (prophos = (R)-1,2-propanediylbis(diphenylphosphine); X = Cl (2a, 2a'), I (4a)) complexes from [{(eta(5)-C(5)Me(5))RhX)(2)-(mu-X)(2)] in methanol is reported (de = 54 and greater than or equal to 98, respectively). The rhodium center is configurationally stable in the iodo complex, but the chloro analogue epimerizes in polar solvents. Complexes 2 and 4 are formed through the dinuclear intermediates [{(eta(5)-C(5)Me(5))RhX(2)}(2)(mu-prophos)] and the monodentate diphosphine complexes [(eta(5)-C(5)Me(5))RhX(2)(prophos)] with high stereoselectivity. The determination of the absolute configuration of 2a and 2a' complexes comes from the X-ray diffraction study of [(eta(5)-C(5)Me(5))RhCl(prophos)]BF4 (2b) obtained from mixtures of 2a and 2a' by anion exchange. In 2b the chiral metal exhibits an S absolute configuration.

引用

页码：2961 / 2966

页数：6

共 49 条

[1]

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[2] CLEAVAGE OF BOTH ALKYL C-H BONDS AND ARYL C-F BONDS AND CONCOMITANT C-C BOND FORMATION IN A PENTAMETHYLCYCLOPENTADIENYLRHODIUM PHOSPHINE COMPLEX - X-RAY STRUCTURE OF [(ETA(5)-C(5)ME(3)[CH2C(6)F(4)P(C6F5)CH2](2)-1,3)RHCL]+BF4- [J].