SELECTIVE SYNTHESIS AND FORMATION MECHANISMS OF TRANS-BENZOYL(CARBAMOYL)PLATINUM(II) AND CIS-BENZOYL(CARBAMOYL)PLATINUM(II) COMPLEXES COORDINATED WITH TERTIARY PHOSPHINE-LIGANDS

被引：16

作者：

HUANG, L ^{[1
]}

OZAWA, F ^{[1
]}

YAMAMOTO, A ^{[1
]}

机构：

[1] TOKYO INST TECHNOL,RESOURCES UTILIZAT RES LAB,MIDORI KU,YOKOHAMA,KANAGAWA 227,JAPAN

来源：

ORGANOMETALLICS | 1990年 / 9卷 / 09期

关键词：

D O I：

10.1021/om00159a033

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

trans-Pt(COPh)Cl(PPh3)2 (1) reacts with secondary amines under CO pressure (10 atm) at room temperature to give cis-Pt(COPh)(CONR2)(PPh3)2 complexes (NR2 = NMe2 (5a), N(CH2)4CH2 (5b), N(CH2)3CH2 (5c), NEt2 (5d)) exclusively, while the same amines react with trans-[Pt(COPh)(CO)(PPh3)2]BF4 (7) under a nitrogen atmosphere to afford trans-Pt(COPh)(CONR2)(PPh3)2 complexes (NR2 = NMe2 = NMe2 (6a), N(CH2)4CH2 (6b), N(CH2)3CH2 (6c), NEt2 (6d)). The isomerization of the trans-benzoylcarbamoyl complexes (6a-d) to their cis isomers (5a-d) in a neat solvent is a slowprocess, but the isomerization is significantly accelerated by addition of amine and CO. On the other hand, benzoylplatinum complexes coordinated with compact and basic PMe3 ligands, trans-Pt(COPh)Cl(PMe3)2 (2) and trans-[Pt(COPh)(acetone)(PMe3)2]BF4 (4), give trans-Pt(COPh)(CONR2)(PMe3)2 (9) exclusively on treatment with CO and the secondary amines. Complex 9 is inert to isomerization to its cis isomer. Formation pathways of trans- and cis-benzoyl(carbamoyl)platinum complexes and their trans-cis isomerization process are examined in detail, and a new type of isomerization pathway involving participation of added CO and amine is proposed. © 1990, American Chemical Society. All rights reserved.

引用

页码：2612 / 2620

页数：9

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