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
Publication type: Journal Article
Publication date: 2013-08-01
scimago Q3
wos Q2
SJR: 0.385
CiteScore: 4.1
Impact factor: 2.4
ISSN: 0022328X, 18728561
Materials Chemistry
Organic Chemistry
Biochemistry
Inorganic Chemistry
Physical and Theoretical Chemistry
Abstract
Reaction of CpRu(cod)Cl with phenylacetylene and AcOH gives an unusual binuclear ruthenium complex CpRu(μ-σ,η3:η3,σ-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-diphenyl-3a,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-1-acetoxy-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.
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Perekalin D. S. et al. 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 // Journal of Organometallic Chemistry. 2013. Vol. 737. pp. 21-25.
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Perekalin D. S., Trifonova E. A., Novikov V. V., Nelyubina Y. V., Kudinov A. R. 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 // Journal of Organometallic Chemistry. 2013. Vol. 737. pp. 21-25.
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TY - JOUR
DO - 10.1016/j.jorganchem.2013.03.043
UR - https://linkinghub.elsevier.com/retrieve/pii/S0022328X13002453
TI - 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
T2 - Journal of Organometallic Chemistry
AU - Perekalin, Dmitry S
AU - Trifonova, Evgeniya A
AU - Novikov, Valentin V
AU - Nelyubina, Yulia V.
AU - Kudinov, Alexander R
PY - 2013
DA - 2013/08/01
PB - Elsevier
SP - 21-25
VL - 737
SN - 0022-328X
SN - 1872-8561
ER -
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@article{2013_Perekalin,
author = {Dmitry S Perekalin and Evgeniya A Trifonova and Valentin V Novikov and Yulia V. Nelyubina and Alexander R Kudinov},
title = {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},
journal = {Journal of Organometallic Chemistry},
year = {2013},
volume = {737},
publisher = {Elsevier},
month = {aug},
url = {https://linkinghub.elsevier.com/retrieve/pii/S0022328X13002453},
pages = {21--25},
doi = {10.1016/j.jorganchem.2013.03.043}
}