Reactions of the cyclopentadienyl ruthenium complexes (C5R5)Ru(cod)Cl and [(C5R5)Ru(MeCN)3]+ (R = H, Me) with phenylacetylene and acetic acid: Unexpected difference in reactivity of CpRu and Cp*Ru complexes

被引：5

作者：

Perekalin, Dmitry S. ^{[1
]}

Trifonova, Evgeniya A. ^{[1
]}

Novikov, Valentin V. ^{[1
]}

Nelyubina, Yulia V. ^{[1
]}

Kudinov, Alexander R. ^{[1
]}

机构：

[1] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Moscow 119991, Russia

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2013年 / 737卷

关键词：

Ruthenium; Cyclopentadienyl; Catalysis; Alkynes; Bridging ligand; Flyover ligand; BOND-CLEAVAGE; ALKYNES; SUBSTITUTION; BIS(CYCLOPENTADIENYL)TITANACYCLOPENTADIENES; METALLACYCLOPENTATRIENE; CYCLOTRIMERIZATION; TRANSFORMATIONS; MECHANISM; LIGANDS; TERMS;

D O I：

10.1016/j.jorganchem.2013.03.043

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of CpRu(cod) Cl with phenylacetylene and AcOH gives an unusual binuclear ruthenium complex CpRu(mu-sigma, eta(3): eta(3), sigma-C6H3Ph3) RuCp (5, 58% yield) with a bridging acyclic flyover ligand C6H3Ph3. Under similar conditions [CpRu(MeCN)(3)](+) undergoes an unexpected cleavage of Cp ligand giving 4,7-diphenyl3a, 7a-dihydroindene (6, 65% yield). In sharp contrast, the pentamethylated congeners Cp*Ru(cod) Cl and [Cp*Ru(MeCN)(3)](+) react with phenylacetylene and AcOH in catalytic fashion giving 1,4-diphenyl-1acetoxy- 1,3-butadiene. The structures of 5 and 6 were established by X-ray diffraction. The mechanism of Cp ligand cleavage was proposed on the basis of DFT calculations. (C) 2013 Elsevier B.V. All rights reserved.

引用

页码：21 / 25

页数：5

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