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

共 27 条

[11] THEORETICAL-STUDIES OF OXIDATIVE ADDITION AND REDUCTIVE ELIMINATION .2. REDUCTIVE COUPLING OF H-H, H-C, AND C-C BONDS FROM PALLADIUM AND PLATINUM COMPLEXES [J].

LOW, JJ ;

GODDARD, WA .

ORGANOMETALLICS, 1986, 5 (04) :609-622

[12] PALLADIUM-PROMOTED DOUBLE-CARBONYLATION REACTIONS - REACTIONS OF ORGANOPALLADIUM COMPOUNDS WITH CARBON-MONOXIDE AND AMINES TO GIVE ALPHA-KETO AMIDES [J].

OZAWA, F ;

SUGIMOTO, T ;

YUASA, Y ;

SANTRA, M ;

YAMAMOTO, T ;

YAMAMOTO, A .

ORGANOMETALLICS, 1984, 3 (05) :683-692

[13] PREPARATION OF TRANS-PD(COCOR)CL(PMEPH2)2 COMPLEXES (R = PH AND ME) AND THEIR REACTIVITIES RELATED TO DOUBLE CARBONYLATION PROMOTED BY PALLADIUM [J].

OZAWA, F ;

SUGIMOTO, T ;

YAMAMOTO, T ;

YAMAMOTO, A .

ORGANOMETALLICS, 1984, 3 (05) :692-697

[14] CATALYTIC DOUBLE CARBONYLATION OF ORGANOHALOGEN COMPOUNDS PROMOTED BY PALLADIUM COMPLEXES [J].

OZAWA, F ;

SOYAMA, H ;

YAMAMOTO, T ;

YAMAMOTO, A .

TETRAHEDRON LETTERS, 1982, 23 (33) :3383-3386

[15] DOUBLE CARBONYLATION OF ALKENES VIA AN AMINOPALLADATION REACTION [J].

OZAWA, F ;

NAKANO, M ;

AOYAMA, I ;

YAMAMOTO, T ;

YAMAMOTO, A .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (05) :382-383

[16] DOUBLE CARBONYLATION REACTIONS OF METHYL-PALLADIUM(II) AND PHENYLPALADIUM(II) COMPLEXES IN THE PRESENCE OF SECONDARY-AMINES AFFORDING ALPHA-KETO AMIDES [J].

OZAWA, F ;

YAMAMOTO, A .

CHEMISTRY LETTERS, 1982, (06) :865-868

[17] PALLADIUM-CATALYZED CARBONYLATION OF AROMATIC-ALDEHYDES AND HYDROCARBONS - A NOVEL SYNTHETIC ROUTE TO ALPHA-KETO AMIDES VIA C-H ACTIVATION [J].

OZAWA, F ;

YAMAGAMI, I ;

NAKANO, M ;

FUJISAWA, F ;

YAMAMOTO, A .

CHEMISTRY LETTERS, 1989, (01) :125-128

[18] PALLADIUM-CATALYZED DOUBLE CARBONYLATION OF ARYL HALIDES TO GIVE ALPHA-KETO AMIDES - MECHANISTIC STUDIES [J].

OZAWA, F ;

SOYAMA, H ;

YANAGIHARA, H ;

AOYAMA, I ;

TAKINO, H ;

IZAWA, K ;

YAMAMOTO, T ;

YAMAMOTO, A .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (11) :3235-3245

[19] PALLADIUM-CATALYZED DOUBLE CARBONYLATION OF ARYL HALIDES AFFORDING ALPHA-KETO AMIDES - APPLICATIONS TO SYNTHESIS OF ISATIN AND QUINOLINE DERIVATIVES [J].

OZAWA, F ;

YANAGIHARA, H ;

YAMAMOTO, A .

JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (03) :415-417

[20] MECHANISMS OF DOUBLE AND SINGLE CARBONYLATION REACTIONS OF ARYL IODIDES CATALYZED BY PALLADIUM COMPLEXES TO GIVE ALPHA-KETO ESTERS AND ESTERS [J].

OZAWA, F ;

KAWASAKI, N ;

OKAMOTO, H ;

YAMAMOTO, T ;

YAMAMOTO, A .

ORGANOMETALLICS, 1987, 6 (08) :1640-1651

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