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 journalArticle

17 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.

LanguageEnglish
Pages3616-3628
Number of pages13
JournalDalton Transactions
Volume2004
Issue number21
Early online date16 Sep 2004
DOIs
Publication statusPublished - 7 Nov 2004
Externally publishedYes

Fingerprint

Ruthenium
Carbon Monoxide
Chemical activation
Electrons
phosphine
Photochemical reactions
Toluene
Isomers
Nuclear magnetic resonance spectroscopy
Hydrogenation
Photons
Catalysts

Cite this

Dunne, John P. ; Blazina, Damir ; Aiken, Stuart ; Carteret, Hilary A. ; Duckett, Simon B. ; Jones, Jonathan A. ; Poli, Rinaldo ; Whitwood, Adrian C. / A combined parahydrogen and theoretical study of H2 activation by 16-electron d8 ruthenium(0) complexes and their subsequent catalytic behaviour. In: Dalton Transactions. 2004 ; Vol. 2004, No. 21. pp. 3616-3628.
@article{b784531b349b45289ca3e8acf6fb68d9,
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.}",
year = "2004",
month = "11",
day = "7",
doi = "10.1039/b410912k",
language = "English",
volume = "2004",
pages = "3616--3628",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "21",

}

A combined parahydrogen and theoretical study of H2 activation by 16-electron d8 ruthenium(0) complexes and their subsequent catalytic behaviour. / Dunne, John P.; Blazina, Damir; Aiken, Stuart; Carteret, Hilary A.; Duckett, Simon B.; Jones, Jonathan A.; Poli, Rinaldo; Whitwood, Adrian C.

In: Dalton Transactions, Vol. 2004, No. 21, 07.11.2004, p. 3616-3628.

Research output: Contribution to journalArticle

TY - JOUR

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.

PY - 2004/11/7

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.

UR - http://www.scopus.com/inward/record.url?scp=9644252671&partnerID=8YFLogxK

UR - http://pubs.rsc.org/en/journals/journalissues/dt#!recentarticles

U2 - 10.1039/b410912k

DO - 10.1039/b410912k

M3 - Article

VL - 2004

SP - 3616

EP - 3628

JO - Dalton Transactions

T2 - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 21

ER -