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

Sripriya K. Seetharaman, Min Chul Chung, Ulrich Englich, Karin Ruhlandt, Michael 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 languageEnglish (US)
Pages (from-to)561-567
Number of pages7
JournalInorganic Chemistry
Volume46
Issue number2
DOIs
StatePublished - Jan 22 2007

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phosphine
Carbon Monoxide
phosphines
methylidyne
Temperature
temperature
Equilibrium constants
Hydrides
Crystal structure
Chemical activation
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Temperature-dependent coordination of phosphine to five-coordinate alkenylruthenium complexes. / Seetharaman, Sripriya K.; Chung, Min Chul; Englich, Ulrich; Ruhlandt, Karin; Sponsler, Michael.

In: Inorganic Chemistry, Vol. 46, No. 2, 22.01.2007, p. 561-567.

Research output: Contribution to journalArticle

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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).",
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AU - Seetharaman, Sripriya K.

AU - Chung, Min Chul

AU - Englich, Ulrich

AU - Ruhlandt, Karin

AU - Sponsler, Michael

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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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