High-pressure infrared studies of rhodium complexes containing thiolate bridge ligands under hydroformylation conditions

被引：46

作者：

Diéguez, M

Claver, C

Masdeu-Bultó, AM

Ruiz, A

van Leeuwen, PWNM

Schoemaker, GC

机构：

[1] Univ Rovira & Virgili, Dept Quim Fis & Inorgan, Tarragona 43005, Spain

[2] Univ Amsterdam, Inst Mol Chem, NL-1018 WV Amsterdam, Netherlands

来源：

ORGANOMETALLICS | 1999年 / 18卷 / 11期

关键词：

D O I：

10.1021/om990003o

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

In situ high-pressure IR spectroscopy studies of the rhodium catalyst systems [Rh-2{mu-S(CH2)(3)N(Me-2)}(2)(COD)(2)]/PR3 (R = Ph, OPh), [Rh-2{mu-S(CH2)(2)S}(COD)(2)]/PPh3, [Rh-2{mu-S(CH2)(4)S}(COD)(2)](2)/PPh3, [Rh-2{mu-XANTOSS}(COD)(2)](2)/PPh3, and [Rh(acac)(CO)(2)]/PR3 (R = Ph, OPh) revealed the presence of mononuclear rhodium hydride species under hydroformylation conditions (80 degrees C, 5-30 bar). The activities and selectivities, obtained during the hydroformylation of l-hexene using these systems as catalyst precursors, can be fully accounted for by the mononuclear species observed. Deuterioformylation experiments using dinuclear [Rh-2{mu-S(CH2)(3)N(Me-2)}(2)(COD)(2)]/PR3 systems lent no support to a dinuclear mechanism.

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页码：2107 / 2115

页数：9

相关论文

共 53 条

[1] PREPARATION OF CARBONYL PHOSPHINE RHODIUM COMPLEXES WITH DITHIOLATE BRIDGES - APPLICATION AS CATALYST PRECURSORS IN THE HYDROFORMYLATION OF 1-HEXENE [J].

AALITI, A ;

MASDEU, AM ;

RUIZ, A ;

CLAVER, C .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1995, 489 (1-2) :101-106

[2] SELECTIVE HYDROFORMYLATION WITH A RECOVERABLE DIRHODIUM MU-THIOLATO COMPLEX [J].

BAYON, JC ;

REAL, J ;

CLAVER, C ;

POLO, A ;

RUIZ, A .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (15) :1056-1057

[3] HOMOGENEOUS HYDROFORMYLATION OF ALKENES WITH HYDRIDOCARBONYLTRIS-(TRIPHENYLPHOSPHINE)RHODIUM(I) AS CATALYST [J].

BROWN, CK ;

WILKINSON, G .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1970, (17) :2753-+

[4] STRUCTURAL CHARACTERIZATION IN SOLUTION OF INTERMEDIATES IN RHODIUM-CATALYZED HYDROFORMYLATION AND THEIR INTERCONVERSION PATHWAYS [J].

BROWN, JM ;

KENT, AG .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1987, (11) :1597-1607

[5] Fluxional processes in asymmetric hydroformylation catalysts [HRhL-L(CO)2] containing C2-symmetric diphosphite ligands [J].

Buisman, GJH ;

van der Veen, LA ;

Kamer, PCJ ;

van Leeuwen, PWNM .

ORGANOMETALLICS, 1997, 16 (26) :5681-5687

[6] HYDRIDORHODIUM DIPHOSPHITE CATALYSTS IN THE ASYMMETRIC HYDROFORMYLATION OF STYRENE [J].

BUISMAN, GJH ;

VOS, EJ ;

KAMER, PCJ ;

VANLEEUWEN, PWNM .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1995, (03) :409-417

[7] (CHELATING DIPHOSPHINE)RHODIUM-CATALYZED DEUTERIOFORMYLATION OF 1-HEXENE - CONTROL OF REGIOCHEMISTRY BY THE KINETIC RATIO OF ALKYLRHODIUM SPECIES FORMED BY HYDRIDE ADDITION TO COMPLEXED ALKENE [J].

CASEY, CP ;

PETROVICH, LM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (22) :6007-6014

[8] Diphosphine and dithiolate rhodium complexes: Characterization of the species under hydroformylation conditions [J].

Castellanos-Paez, A ;

Castillon, S ;

Claver, C ;

van Leeuwen, PWNM ;

de Lange, WGJ .

ORGANOMETALLICS, 1998, 17 (12) :2543-2552

[9] Synthesis of rhodium(I) complexes with the new dithiol chiral ligand (+)-trans-2,3-bis(mercaptomethyl)-bicyclo[2.2.2]octane (H2BCOS) - Their application as catalysts precursors in the styrene hydroformylation [J].

CastellanosPaez, A ;

Castillon, S ;

Claver, C .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 539 (1-2) :1-7

[10] ASYMMETRIC HYDROFORMYLATION OF STYRENE BY RHODIUM(1) CATALYSTS WITH CHIRAL LIGANDS CONTAINING SULFUR DONORS [J].

CLAVER, C ;

CASTILLON, S ;

RUIZ, N ;

DELOGU, G ;

FABBRI, D ;

GLADIALI, S .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1993, (24) :1833-1834

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