The photochemical generation of novel neutral mononuclear ruthenium complexes and their reactivity

Andrew J. Edwards; Nicholas E. Leadbeater; Jack Lewis; Paul R. Raithby

doi:10.1016/0022-328X(95)05440-Z

The photochemical generation of novel neutral mononuclear ruthenium complexes and their reactivity

Andrew J. Edwards, Nicholas E. Leadbeater, Jack Lewis, Paul R. Raithby

University of Cambridge

Research output: Contribution to journal › Article › peer-review

Abstract

The room-temperature photolysis of Ru₃(CO)₁₂ (1) in dichloromethane under a flow of ethylene affords the highly reactive complex Ru(CO)₄(C₂H₄) (2) in a quantitative yield. The addition of MeCN to the reaction mixture, while the photolytic conditions and the ethylene flow are maintained, gives Ru(CO)₃(C₂H₄)(NCMe) (3). If the irradiation is continued but the ethylene flow stopped, a different product, namely Ru(CO)₃(NCMe)₂ (4) is obtained. The addition of an excess of triphenylphosphine to a dichloromethane solution of 2 in the absence of ethylene and of light gives two phosphine-substituted products: Ru(CO)₄(PPh₃) (5) and Ru(CO)₃(PPh₃)₂ (6). Under similar conditions, 3 affords 6 and the cluster Ru₃(CO)₉(PPh₃)₃ (7) while, if MeCN is added instead of PPh₃, the reactive cluster Ru₃(CO)₉(NCMe)₃ (8) is obtained. If an excess of acrylonitrile is used instead of ethylene, the photolysis of 1 in dichloromethane yields Ru(CO)₄(NCCHCH₂) (9) which reacts under photolytic conditions but in the absence of an excess of acrylonitrile with MeCN to give Ru(CO)₃(NCCHCH₂)(MeCN) (10) and this product reacts with a second equivalent of acrylonitrile to afford Ru(CO)₃(NCCHCH₂)₂ (11). All the products have been characterized by IR spectroscopy and their structures established from symmetry considerations.

Original language	English
Pages (from-to)	15-20
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	503
Issue number	1
DOIs	https://doi.org/10.1016/0022-328X(95)05440-Z
Publication status	Published - 1 Nov 1995

Funding

We acknowledge the support of the EPSRC for A.J.E. and N.E.L. We are grateful to Johnson Matthey plc for the loan of ruthenium trichloride.

Funders	Funder number
Engineering and Physical Sciences Research Council

Keywords

Carbonyl
Ethylene
Nitrile
Photochemical synthesis
Ruthenium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/0022-328X(95)05440-Z

Cite this

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title = "The photochemical generation of novel neutral mononuclear ruthenium complexes and their reactivity",

abstract = "The room-temperature photolysis of Ru3(CO)12 (1) in dichloromethane under a flow of ethylene affords the highly reactive complex Ru(CO)4(C2H4) (2) in a quantitative yield. The addition of MeCN to the reaction mixture, while the photolytic conditions and the ethylene flow are maintained, gives Ru(CO)3(C2H4)(NCMe) (3). If the irradiation is continued but the ethylene flow stopped, a different product, namely Ru(CO)3(NCMe)2 (4) is obtained. The addition of an excess of triphenylphosphine to a dichloromethane solution of 2 in the absence of ethylene and of light gives two phosphine-substituted products: Ru(CO)4(PPh3) (5) and Ru(CO)3(PPh3)2 (6). Under similar conditions, 3 affords 6 and the cluster Ru3(CO)9(PPh3)3 (7) while, if MeCN is added instead of PPh3, the reactive cluster Ru3(CO)9(NCMe)3 (8) is obtained. If an excess of acrylonitrile is used instead of ethylene, the photolysis of 1 in dichloromethane yields Ru(CO)4(NCCHCH2) (9) which reacts under photolytic conditions but in the absence of an excess of acrylonitrile with MeCN to give Ru(CO)3(NCCHCH2)(MeCN) (10) and this product reacts with a second equivalent of acrylonitrile to afford Ru(CO)3(NCCHCH2)2 (11). All the products have been characterized by IR spectroscopy and their structures established from symmetry considerations.",

keywords = "Carbonyl, Ethylene, Nitrile, Photochemical synthesis, Ruthenium",

author = "Edwards, {Andrew J.} and Leadbeater, {Nicholas E.} and Jack Lewis and Raithby, {Paul R.}",

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AU - Edwards, Andrew J.

AU - Leadbeater, Nicholas E.

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AU - Raithby, Paul R.

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Y1 - 1995/11/1

N2 - The room-temperature photolysis of Ru3(CO)12 (1) in dichloromethane under a flow of ethylene affords the highly reactive complex Ru(CO)4(C2H4) (2) in a quantitative yield. The addition of MeCN to the reaction mixture, while the photolytic conditions and the ethylene flow are maintained, gives Ru(CO)3(C2H4)(NCMe) (3). If the irradiation is continued but the ethylene flow stopped, a different product, namely Ru(CO)3(NCMe)2 (4) is obtained. The addition of an excess of triphenylphosphine to a dichloromethane solution of 2 in the absence of ethylene and of light gives two phosphine-substituted products: Ru(CO)4(PPh3) (5) and Ru(CO)3(PPh3)2 (6). Under similar conditions, 3 affords 6 and the cluster Ru3(CO)9(PPh3)3 (7) while, if MeCN is added instead of PPh3, the reactive cluster Ru3(CO)9(NCMe)3 (8) is obtained. If an excess of acrylonitrile is used instead of ethylene, the photolysis of 1 in dichloromethane yields Ru(CO)4(NCCHCH2) (9) which reacts under photolytic conditions but in the absence of an excess of acrylonitrile with MeCN to give Ru(CO)3(NCCHCH2)(MeCN) (10) and this product reacts with a second equivalent of acrylonitrile to afford Ru(CO)3(NCCHCH2)2 (11). All the products have been characterized by IR spectroscopy and their structures established from symmetry considerations.

AB - The room-temperature photolysis of Ru3(CO)12 (1) in dichloromethane under a flow of ethylene affords the highly reactive complex Ru(CO)4(C2H4) (2) in a quantitative yield. The addition of MeCN to the reaction mixture, while the photolytic conditions and the ethylene flow are maintained, gives Ru(CO)3(C2H4)(NCMe) (3). If the irradiation is continued but the ethylene flow stopped, a different product, namely Ru(CO)3(NCMe)2 (4) is obtained. The addition of an excess of triphenylphosphine to a dichloromethane solution of 2 in the absence of ethylene and of light gives two phosphine-substituted products: Ru(CO)4(PPh3) (5) and Ru(CO)3(PPh3)2 (6). Under similar conditions, 3 affords 6 and the cluster Ru3(CO)9(PPh3)3 (7) while, if MeCN is added instead of PPh3, the reactive cluster Ru3(CO)9(NCMe)3 (8) is obtained. If an excess of acrylonitrile is used instead of ethylene, the photolysis of 1 in dichloromethane yields Ru(CO)4(NCCHCH2) (9) which reacts under photolytic conditions but in the absence of an excess of acrylonitrile with MeCN to give Ru(CO)3(NCCHCH2)(MeCN) (10) and this product reacts with a second equivalent of acrylonitrile to afford Ru(CO)3(NCCHCH2)2 (11). All the products have been characterized by IR spectroscopy and their structures established from symmetry considerations.

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KW - Ethylene

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ER -

The photochemical generation of novel neutral mononuclear ruthenium complexes and their reactivity

Abstract

Funding

Keywords

ASJC Scopus subject areas

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