Synthesis and reactivity of the ruthenium cyclopropenyl complex with a Tp ligand

被引：36

作者：

Lo, YH ^{[1
]}

Lin, YC ^{[1
]}

Lee, GH ^{[1
]}

Wang, Y ^{[1
]}

机构：

[1] Natl Taiwan Univ, Dept Chem, Taipei 106, Taiwan

来源：

ORGANOMETALLICS | 1999年 / 18卷 / 06期

关键词：

D O I：

10.1021/om980752q

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Treatment of Tp(PPh3)(2)Ru-C equivalent to C-Ph (1) with ICH2CN affords the cationic vinylidene complex [Tp(PPh3)(2)Ru=C=C(Ph)CH2CN]I (2). The neutral ruthenium cyclopropenyl complex Tp(PPh3)(2)RuC=C(Ph)CHCN (3) is then prepared by deprotonation of 2. Facile displacement of one phosphine ligand of 3 by CH3CN yields a diastereomeric mixture in a 4:1 ratio of the substitution product, Tp(PPh3)(CH3CN)RuC=C(Ph)CHCN (4). The cyclopropenyl ring in 3 and 4 is susceptible to ring opening by electrophiles such as CF3COOH, Ph3CPF6, and HgCl2. The substitution reaction of 3 with pyrazole is followed by an intramolecular nucleophilic addition of the nitrogen atom at the or-carbon atom to afford the metallacyclic complex, Tp(PPh3)Ru(C3H3NN)C=C (Ph)CH2CN (8a). The re action of 3 with CO in the presence of MeOH gives Tp(PPh3)(CO)RuC(OMe)=C(Ph)CH2CN (9). The reaction of CF3COOH with 9 yields Tp(PPh3)(CO)RuC(O)CH(Ph)CH2CN (11). The structures of 8a and 11 have been determined by X-ray diffraction analysis.

引用

页码：982 / 988

页数：7

共 34 条

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