A combined parahydrogen and theoretical study of H2 activation by 16-electron d8 ruthenium(0) complexes and their subsequent catalytic behaviour

John P. Dunne; Damir Blazina; Stuart Aiken; Hilary A. Carteret; Simon B. Duckett; Jonathan A. Jones; Rinaldo Poli; Adrian C. Whitwood

doi:10.1039/b410912k

A combined parahydrogen and theoretical study of H₂ activation by 16-electron d⁸ ruthenium(0) complexes and their subsequent catalytic behaviour

John P. Dunne, Damir Blazina, Stuart Aiken, Hilary A. Carteret, Simon B. Duckett, Jonathan A. Jones, Rinaldo Poli, Adrian C. Whitwood

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

21 Citations (Scopus)

Abstract

The photochemical reaction of Ru(CO)₃(L)₂, where L = PPh₃, PMe₃, PCy₃ and P(p-tolyl)₃ with parahydrogen (p-H₂) has been studied by in-situ NMR spectroscopy and shown to result in two competing processes. The first of these involves loss of CO and results in the formation of the cis-cis-trans-L isomer of Ru(CO)₂(L)₂(H)₂, while in the second, a single photon induces loss of both CO and L and leads to the formation of cis-cis-cis Ru(CO)₂(L)₂(H)₂ and Ru(CO)₂(L) (solvent)(H)₂ where solvent = toluene, THF and pyridine (py). In the case of L = PPh₃, cis-cis-trans-L Ru(CO)₂(L) ₂(H)₂ is shown to be an effective hydrogenation catalyst with rate limiting phosphine dissociation proceeding at a rate of 2.2 s ^-1 in pyridine at 355 K. Theoretical calculations and experimental observations show that H₂ addition to the Ru(CO)₂(L) ₂ proceeds to form cis-cis-trans-L Ru(CO)₂(L) ₂(H)₂ as the major product via addition over the π-accepting OC-Ru-CO axis.

Original language	English
Pages (from-to)	3616-3628
Number of pages	13
Journal	Dalton Transactions
Volume	2004
Issue number	21
Early online date	16 Sep 2004
DOIs	https://doi.org/10.1039/b410912k
Publication status	Published - 7 Nov 2004
Externally published	Yes

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title = "A combined parahydrogen and theoretical study of H2 activation by 16-electron d8 ruthenium(0) complexes and their subsequent catalytic behaviour",

abstract = "The photochemical reaction of Ru(CO)3(L)2, where L = PPh3, PMe3, PCy3 and P(p-tolyl)3 with parahydrogen (p-H2) has been studied by in-situ NMR spectroscopy and shown to result in two competing processes. The first of these involves loss of CO and results in the formation of the cis-cis-trans-L isomer of Ru(CO)2(L)2(H)2, while in the second, a single photon induces loss of both CO and L and leads to the formation of cis-cis-cis Ru(CO)2(L)2(H)2 and Ru(CO)2(L) (solvent)(H)2 where solvent = toluene, THF and pyridine (py). In the case of L = PPh3, cis-cis-trans-L Ru(CO)2(L) 2(H)2 is shown to be an effective hydrogenation catalyst with rate limiting phosphine dissociation proceeding at a rate of 2.2 s -1 in pyridine at 355 K. Theoretical calculations and experimental observations show that H2 addition to the Ru(CO)2(L) 2 proceeds to form cis-cis-trans-L Ru(CO)2(L) 2(H)2 as the major product via addition over the π-accepting OC-Ru-CO axis.",

author = "Dunne, {John P.} and Damir Blazina and Stuart Aiken and Carteret, {Hilary A.} and Duckett, {Simon B.} and Jones, {Jonathan A.} and Rinaldo Poli and Whitwood, {Adrian C.}",

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T1 - A combined parahydrogen and theoretical study of H2 activation by 16-electron d8 ruthenium(0) complexes and their subsequent catalytic behaviour

AU - Dunne, John P.

AU - Blazina, Damir

AU - Aiken, Stuart

AU - Carteret, Hilary A.

AU - Duckett, Simon B.

AU - Jones, Jonathan A.

AU - Poli, Rinaldo

AU - Whitwood, Adrian C.

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Y1 - 2004/11/7

N2 - The photochemical reaction of Ru(CO)3(L)2, where L = PPh3, PMe3, PCy3 and P(p-tolyl)3 with parahydrogen (p-H2) has been studied by in-situ NMR spectroscopy and shown to result in two competing processes. The first of these involves loss of CO and results in the formation of the cis-cis-trans-L isomer of Ru(CO)2(L)2(H)2, while in the second, a single photon induces loss of both CO and L and leads to the formation of cis-cis-cis Ru(CO)2(L)2(H)2 and Ru(CO)2(L) (solvent)(H)2 where solvent = toluene, THF and pyridine (py). In the case of L = PPh3, cis-cis-trans-L Ru(CO)2(L) 2(H)2 is shown to be an effective hydrogenation catalyst with rate limiting phosphine dissociation proceeding at a rate of 2.2 s -1 in pyridine at 355 K. Theoretical calculations and experimental observations show that H2 addition to the Ru(CO)2(L) 2 proceeds to form cis-cis-trans-L Ru(CO)2(L) 2(H)2 as the major product via addition over the π-accepting OC-Ru-CO axis.

AB - The photochemical reaction of Ru(CO)3(L)2, where L = PPh3, PMe3, PCy3 and P(p-tolyl)3 with parahydrogen (p-H2) has been studied by in-situ NMR spectroscopy and shown to result in two competing processes. The first of these involves loss of CO and results in the formation of the cis-cis-trans-L isomer of Ru(CO)2(L)2(H)2, while in the second, a single photon induces loss of both CO and L and leads to the formation of cis-cis-cis Ru(CO)2(L)2(H)2 and Ru(CO)2(L) (solvent)(H)2 where solvent = toluene, THF and pyridine (py). In the case of L = PPh3, cis-cis-trans-L Ru(CO)2(L) 2(H)2 is shown to be an effective hydrogenation catalyst with rate limiting phosphine dissociation proceeding at a rate of 2.2 s -1 in pyridine at 355 K. Theoretical calculations and experimental observations show that H2 addition to the Ru(CO)2(L) 2 proceeds to form cis-cis-trans-L Ru(CO)2(L) 2(H)2 as the major product via addition over the π-accepting OC-Ru-CO axis.

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A combined parahydrogen and theoretical study of H₂ activation by 16-electron d⁸ ruthenium(0) complexes and their subsequent catalytic behaviour

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