Advanced

Mechanisms of concurrent hydride migration processes in a triruthenium cluster capped by a phenylphosphinidene (PPh) ligand

Deeming, AJ; Forth, CS; Hyder, MI; Kabir, SE; Nordlander, Ebbe LU ; Rodgers, F and Ullmann, B (2005) In European Journal of Inorganic Chemistry p.4352-4360
Abstract
Two methods were used to synthesise [Ru-3(mu-H)(2)(mu(3)-PPh)-(CO)(7) (mu-dppm)] (3) (dppm = Ph2PCH2PPh2), the subject of this paper. Treatment of [Ru-3(CO)(10)(mu-dppm)] (1) with phenylphosphane in refluxing THF gave both [Ru-3(mu-H)(2)(mu-PHPh)-(CO)(8)(mu-dppm)] (2) and [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(7)(mu-dppm)] (3). Cluster 2 converts to 3 in refluxing THF. Alternatively the phenylphosphinidene cluster [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(9)] (4), prepared by the reported method of treating [Ru-3(CO)(12)] with phenylphosphane, reacts with dppm to produce cluster 3. The single-crystal X-ray structures of 2 and 3 are reported. Hydride mobility in [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(7)(mu-dppm)] (3) was analysed by variable-temperature H-1 and... (More)
Two methods were used to synthesise [Ru-3(mu-H)(2)(mu(3)-PPh)-(CO)(7) (mu-dppm)] (3) (dppm = Ph2PCH2PPh2), the subject of this paper. Treatment of [Ru-3(CO)(10)(mu-dppm)] (1) with phenylphosphane in refluxing THF gave both [Ru-3(mu-H)(2)(mu-PHPh)-(CO)(8)(mu-dppm)] (2) and [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(7)(mu-dppm)] (3). Cluster 2 converts to 3 in refluxing THF. Alternatively the phenylphosphinidene cluster [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(9)] (4), prepared by the reported method of treating [Ru-3(CO)(12)] with phenylphosphane, reacts with dppm to produce cluster 3. The single-crystal X-ray structures of 2 and 3 are reported. Hydride mobility in [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(7)(mu-dppm)] (3) was analysed by variable-temperature H-1 and P-31(H-1) NMR methods. The variations in the spectra with temperature could not be interpreted by a single process, several of which were explored and which gave inadequately matching computed and experimental spectra. However, the spectra were successfully analysed by two concurrent processes, both involving the migration of hydride ligands between Ru-Ru edges. The faster process leads to the exchange of the nonequivalent phosphorus nuclei but not hydride exchange, whereas the hydrides are also exchanged in the slower process. Both processes require hydride ligand migration from one Ru-Ru edge to a vacant one. The hydride ligand bridging the same pair of ruthenium atoms as the dppm ligand is the slower to migrate. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
clusters, ruthenium, dynamic mobility, hydrides, kinetics
in
European Journal of Inorganic Chemistry
issue
21
pages
4352 - 4360
publisher
John Wiley & Sons
external identifiers
  • wos:000233297800013
  • scopus:27744437034
ISSN
1099-0682
DOI
10.1002/ejic.200400892
language
English
LU publication?
yes
id
3645061d-7e5b-4196-ad91-1ce285147945 (old id 213211)
date added to LUP
2007-08-17 15:36:28
date last changed
2017-01-01 05:00:16
@article{3645061d-7e5b-4196-ad91-1ce285147945,
  abstract     = {Two methods were used to synthesise [Ru-3(mu-H)(2)(mu(3)-PPh)-(CO)(7) (mu-dppm)] (3) (dppm = Ph2PCH2PPh2), the subject of this paper. Treatment of [Ru-3(CO)(10)(mu-dppm)] (1) with phenylphosphane in refluxing THF gave both [Ru-3(mu-H)(2)(mu-PHPh)-(CO)(8)(mu-dppm)] (2) and [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(7)(mu-dppm)] (3). Cluster 2 converts to 3 in refluxing THF. Alternatively the phenylphosphinidene cluster [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(9)] (4), prepared by the reported method of treating [Ru-3(CO)(12)] with phenylphosphane, reacts with dppm to produce cluster 3. The single-crystal X-ray structures of 2 and 3 are reported. Hydride mobility in [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(7)(mu-dppm)] (3) was analysed by variable-temperature H-1 and P-31(H-1) NMR methods. The variations in the spectra with temperature could not be interpreted by a single process, several of which were explored and which gave inadequately matching computed and experimental spectra. However, the spectra were successfully analysed by two concurrent processes, both involving the migration of hydride ligands between Ru-Ru edges. The faster process leads to the exchange of the nonequivalent phosphorus nuclei but not hydride exchange, whereas the hydrides are also exchanged in the slower process. Both processes require hydride ligand migration from one Ru-Ru edge to a vacant one. The hydride ligand bridging the same pair of ruthenium atoms as the dppm ligand is the slower to migrate.},
  author       = {Deeming, AJ and Forth, CS and Hyder, MI and Kabir, SE and Nordlander, Ebbe and Rodgers, F and Ullmann, B},
  issn         = {1099-0682},
  keyword      = {clusters,ruthenium,dynamic mobility,hydrides,kinetics},
  language     = {eng},
  number       = {21},
  pages        = {4352--4360},
  publisher    = {John Wiley & Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {Mechanisms of concurrent hydride migration processes in a triruthenium cluster capped by a phenylphosphinidene (PPh) ligand},
  url          = {http://dx.doi.org/10.1002/ejic.200400892},
  year         = {2005},
}