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
收藏
页码：21 / 25
页数：5
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