Temperature-dependent coordination of phosphine to five-coordinate alkenylruthenium complexes

Sripriya K. Seetharaman; Min Chul Chung; Ulrich Englich; Karin Ruhlandt-Senge; Michael B. Sponsler

doi:10.1021/ic061389f

Temperature-dependent coordination of phosphine to five-coordinate alkenylruthenium complexes

Sripriya K. Seetharaman, Min Chul Chung, Ulrich Englich, Karin Ruhlandt-Senge, Michael B. Sponsler

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Abstract

The red, five-coordinate complexes Ru(CO)Cl(PPh₃) ₂(CH=CHPh) and [Ru(CO)Cl(PPh₃)₂] ₂(μ-CH=CHC₆H₄CH= CH) undergo reversible coordination of PPh₃ at low temperature to produce the pale yellow, six-coordinate complexes Ru(CO)Cl(PPh₃)₃(CH=CHPh) and [Ru(CO)Cl(PPh₃)₃]₂(μ-CH=CHC ₆H₄CH=CH). X-ray crystal structures of the latter complex and of the hydride complex RuH(CO)Cl(PPh₃)₃ were obtained. ¹H and ³¹P NMR spectra between 20 and -70°C exhibit large changes in both equilibrium constants and dynamic effects. Thermodynamic parameters, ΔH = -17.5 ± 2.0 kcal/mol and ΔS = -57.5 ± 7.6 eu, were obtained for PPh₃ coordination to the monoruthenium complex, and activation parameters, ΔH^‡ = 20.6 ± 0.7 kcal/mol and ΔS^‡ = 41.6 ± 2.0 eu, were obtained for the reverse decoordination. Coordination of PPh₃ was not observed upon cooling of the shorter bridged complex, [Ru(CO)Cl(PPh ₃)₂]₂(μ-CH=CHCH=CH).

Original language	English (US)
Pages (from-to)	561-567
Number of pages	7
Journal	Inorganic Chemistry
Volume	46
Issue number	2
DOIs	https://doi.org/10.1021/ic061389f
State	Published - Jan 22 2007

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{c0ad63ec5abc4b16b32c034e9795a01d,

title = "Temperature-dependent coordination of phosphine to five-coordinate alkenylruthenium complexes",

abstract = "The red, five-coordinate complexes Ru(CO)Cl(PPh3) 2(CH=CHPh) and [Ru(CO)Cl(PPh3)2] 2(μ-CH=CHC6H4CH= CH) undergo reversible coordination of PPh3 at low temperature to produce the pale yellow, six-coordinate complexes Ru(CO)Cl(PPh3)3(CH=CHPh) and [Ru(CO)Cl(PPh3)3]2(μ-CH=CHC 6H4CH=CH). X-ray crystal structures of the latter complex and of the hydride complex RuH(CO)Cl(PPh3)3 were obtained. 1H and 31P NMR spectra between 20 and -70°C exhibit large changes in both equilibrium constants and dynamic effects. Thermodynamic parameters, ΔH = -17.5 ± 2.0 kcal/mol and ΔS = -57.5 ± 7.6 eu, were obtained for PPh3 coordination to the monoruthenium complex, and activation parameters, ΔH‡ = 20.6 ± 0.7 kcal/mol and ΔS‡ = 41.6 ± 2.0 eu, were obtained for the reverse decoordination. Coordination of PPh3 was not observed upon cooling of the shorter bridged complex, [Ru(CO)Cl(PPh 3)2]2(μ-CH=CHCH=CH).",

author = "Seetharaman, {Sripriya K.} and Chung, {Min Chul} and Ulrich Englich and Karin Ruhlandt-Senge and Sponsler, {Michael B.}",

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T1 - Temperature-dependent coordination of phosphine to five-coordinate alkenylruthenium complexes

AU - Seetharaman, Sripriya K.

AU - Chung, Min Chul

AU - Englich, Ulrich

AU - Ruhlandt-Senge, Karin

AU - Sponsler, Michael B.

PY - 2007/1/22

Y1 - 2007/1/22

N2 - The red, five-coordinate complexes Ru(CO)Cl(PPh3) 2(CH=CHPh) and [Ru(CO)Cl(PPh3)2] 2(μ-CH=CHC6H4CH= CH) undergo reversible coordination of PPh3 at low temperature to produce the pale yellow, six-coordinate complexes Ru(CO)Cl(PPh3)3(CH=CHPh) and [Ru(CO)Cl(PPh3)3]2(μ-CH=CHC 6H4CH=CH). X-ray crystal structures of the latter complex and of the hydride complex RuH(CO)Cl(PPh3)3 were obtained. 1H and 31P NMR spectra between 20 and -70°C exhibit large changes in both equilibrium constants and dynamic effects. Thermodynamic parameters, ΔH = -17.5 ± 2.0 kcal/mol and ΔS = -57.5 ± 7.6 eu, were obtained for PPh3 coordination to the monoruthenium complex, and activation parameters, ΔH‡ = 20.6 ± 0.7 kcal/mol and ΔS‡ = 41.6 ± 2.0 eu, were obtained for the reverse decoordination. Coordination of PPh3 was not observed upon cooling of the shorter bridged complex, [Ru(CO)Cl(PPh 3)2]2(μ-CH=CHCH=CH).

AB - The red, five-coordinate complexes Ru(CO)Cl(PPh3) 2(CH=CHPh) and [Ru(CO)Cl(PPh3)2] 2(μ-CH=CHC6H4CH= CH) undergo reversible coordination of PPh3 at low temperature to produce the pale yellow, six-coordinate complexes Ru(CO)Cl(PPh3)3(CH=CHPh) and [Ru(CO)Cl(PPh3)3]2(μ-CH=CHC 6H4CH=CH). X-ray crystal structures of the latter complex and of the hydride complex RuH(CO)Cl(PPh3)3 were obtained. 1H and 31P NMR spectra between 20 and -70°C exhibit large changes in both equilibrium constants and dynamic effects. Thermodynamic parameters, ΔH = -17.5 ± 2.0 kcal/mol and ΔS = -57.5 ± 7.6 eu, were obtained for PPh3 coordination to the monoruthenium complex, and activation parameters, ΔH‡ = 20.6 ± 0.7 kcal/mol and ΔS‡ = 41.6 ± 2.0 eu, were obtained for the reverse decoordination. Coordination of PPh3 was not observed upon cooling of the shorter bridged complex, [Ru(CO)Cl(PPh 3)2]2(μ-CH=CHCH=CH).

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Temperature-dependent coordination of phosphine to five-coordinate alkenylruthenium complexes

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