MECHANISM OF THE HYDROGENATION OF PHENYLACETYLENE CATALYZED BY [IR(COD)(ETA(2)-IPR2PCH2CH2OME)]BF4

被引：49

作者：

ESTERUELAS, MA

LOPEZ, AM

ORO, LA

PEREZ, A

SCHULZ, M

WERNER, H

机构：

[1] UNIV ZARAGOZA,DEPT QUIM INORGAN,INST CIENCIA MAT ARAGON,CSIC,E-50009 ZARAGOZA,SPAIN

[2] UNIV WURZBURG,INST ANORGAN CHEM,W-8700 WURZBURG,GERMANY

来源：

ORGANOMETALLICS | 1993年 / 12卷 / 05期

关键词：

D O I：

10.1021/om00029a044

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis of the mononuclear complexes of formulas IrCl(COD)(iPr2PCH2CH2OMe) (1) (COD = 1,5-cyclooctadiene), IrCl(COD)(iPr2PCH2CH2NMe2) (2), [Ir(diolefin) (eta2-iPr2PCH2-CH2OMe)]BF4(diolefin = COD (3), TFB (5) (TFB = tetrafluorobenzobarrelene)), [Ir(diolefin)-(eta2-iPr2PCH2CH2NMe2)]BF4 (diolefin = COD (4), TFB (6)), [IrH(C2Ph)(COD)(eta2-iPr2PCH2-CH2OMe)]BF4 (7), and [IrH2(COD)(eta2-iPr2PCH2CH2OMe)BF4 (8) are described. The X-ray crystal structure of 3 has been determined (monoclinic space group P2(1)/n (No. 14) with a = 8.466(3) angstrom, b = 9.004(3) angstrom, c = 27.052(13) angstrom, beta = 97.71(2)-degrees, and Z = 4). 3 is found to be a very active and highly selective catalyst for the hydrogenation of phenylacetylene to styrene. Although the hydrido-alkynyl-diolefin compound 7 is the main species under catalytic conditions, the reaction proceeds via the dihydrido-diolefin intermediate 8 according to the following set of reactions: 8 + H-2 half arrow right over half arrow left [IrH(CH=CHPh)(COD)(eta2-iPr2PCH2CH2OMe)]BF4 (9) and 9 + H-2 --> 8 + PhCH=CH2 where the reaction between 9 and molecular hydrogen is the rate-determining step. The catalytic activity of 3-6 in the hydrogenation of olefins is also reported.

引用

页码：1823 / 1830

页数：8

共 26 条

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