RHODIUM-MEDIATED STOICHIOMETRIC P=C BOND-CLEAVAGE AND CATALYTIC ISOMERIZATION IN PHOSPHACUMULENES

被引：22

作者：

DAVID, MA

PAISNER, SN

GLUECK, DS

机构：

[1] Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 01期

关键词：

D O I：

10.1021/om00001a007

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of Rh(PCy(3))(2)Cl (4a, Cy = cyclo-C6H11 with the phosphacumulenes Mes*P=C=X (X = O (1) X = NPh (2); Mes* = 2,4,6-(t-Bu)(3)C6H2) results in P=C bond cleavage to form [2,4-(t-Bu)(2)C6H2(6-CMe(2)CH(2)PH)](5) and trans-Rh(PCy(3))(2)Cl(CX) (6, X = O; 7,X = NPh), respectively. In contrast, 4a and related Rh(I) PPh(3) complexes are catalyst precursors for the rearrangement of Mes*P=C=CPh(2) 13) to its isomer [2,4-(t-Bu)(2)C6H2(6-CMe(2)CH(2)PCH=CPh(2))] (8); the intermediate [Rh(PCy(3))[eta(2)(P,C)-Mes*P=C=CPh(2)]Cl](n) (9a), which is itself an active catalyst for the isomerization, was isolated and characterized spectroscopically.

引用

页码：17 / 19

页数：3

共 19 条

[1] DIFFERENT MODES OF HYDROGEN MIGRATION IN REACTIONS OF DIPHOSPHAALLENE, ARP=C=PAR (AR = 2,4,6-BU(T)3C6H2) WITH [W(CO)5(THF)] AND [FE3(CO)12].CRYSTAL AND MOLECULAR-STRUCTURE OF [FE2(CO)6(ARP=CHPCH2(CME2)C6H2BU(T)2] [J].