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Syntheses and fluxional processes of diphenyl(2-thienyl)phosphane derivatives of triosmium clusters

Kiriakidou-Kazemifar, Nitsa LU ; Stchedroff, M ; Mottalib, M A ; Selva, S ; Monari, M and Nordlander, Ebbe LU (2006) In European Journal of Inorganic Chemistry p.2058-2068
Abstract
Thermal treatment of [OS3(CO)(12)] with diphenyl(2-thienyl)phosphane, Ph(2)p(C4H3S), results in the formation of [Os-3(CO)(12-x){Ph2P(C4H3S)}(x)] (x = 1-3, 1-3), but no C-H bond activation was observed. Reaction of [H2Os3(CO)(10)] with diphenyl(2-thienyl)phosphane at ambient temperature affords [HOs3(mu-H)(CO)(10){Ph2P(C4H3S}] (4), but when the same reaction is repeated at elevated temperatures, the cyclometallated species [(mu-H)Os-3(CO)(9){mu(3)-Ph(2)p(C4H2S)}] (5) and [mu-H) Os-3(CO)(8){mu 3-Ph2P(C4H2S)}(Ph2P(C4H3S)}] (6) are formed. In addition, two more products, tentatively assigned as [(mu-H)Os-3(CO)(6()mu(3)-Ph2P(C4H2S)}{mu-Ph2P(C4H3S)}{Ph2P-(C4H3S)}] (7) and [(mu-H)Os-3 (CO)(7) {mu-Ph2P(C4H2S)}]... (More)
Thermal treatment of [OS3(CO)(12)] with diphenyl(2-thienyl)phosphane, Ph(2)p(C4H3S), results in the formation of [Os-3(CO)(12-x){Ph2P(C4H3S)}(x)] (x = 1-3, 1-3), but no C-H bond activation was observed. Reaction of [H2Os3(CO)(10)] with diphenyl(2-thienyl)phosphane at ambient temperature affords [HOs3(mu-H)(CO)(10){Ph2P(C4H3S}] (4), but when the same reaction is repeated at elevated temperatures, the cyclometallated species [(mu-H)Os-3(CO)(9){mu(3)-Ph(2)p(C4H2S)}] (5) and [mu-H) Os-3(CO)(8){mu 3-Ph2P(C4H2S)}(Ph2P(C4H3S)}] (6) are formed. In addition, two more products, tentatively assigned as [(mu-H)Os-3(CO)(6()mu(3)-Ph2P(C4H2S)}{mu-Ph2P(C4H3S)}{Ph2P-(C4H3S)}] (7) and [(mu-H)Os-3 (CO)(7) {mu-Ph2P(C4H2S)}] (4)tPh(2)P(C(4)H3(S)))(Ph2P(C4H3S))] (8) are obtained. The dynamic behaviours of 2, 5 and 6 have been studied by variable-temperature (VT) and H-1 P-31{H-1} NMR spectroscopy. The VT P-31{H-1} NMR spectra of [Os-3(CO)(10){Ph2P(C4H3S)}(2)] (2) demonstrate that a mixture of two isomers, which are in rapid exchange at room temperature, is present and that the less common cis-trans isomer, whose structure has been determined by X-ray crystallography, is favoured for this cluster. The VT H-1 NMR spectra of 5 indicate the presence of two isomers which are proposed to arise from an oscillation of the sigma,eta(2)-vinyl group of the thienyl moiety between two metal atoms. A similar fluxional process is proposed to occur in 6 and the assignment of the room-temperature structure(s) of this cluster was confirmed by H-1-Os-187 2D HMQC spectroscopy. In addition to 2, the solid-state structures of 3, 5 and 6 have been determined by X-ray crystallography. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006. (Less)
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organization
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type
Contribution to journal
publication status
published
subject
keywords
hydrodesulfurisation, fluxionality, cluster, thienylphosphane
in
European Journal of Inorganic Chemistry
issue
10
pages
2058 - 2068
publisher
John Wiley and Sons
external identifiers
  • wos:000237998200018
  • scopus:33646917232
ISSN
1099-0682
DOI
10.1002/ejic.200501141
language
English
LU publication?
yes
id
916101b6-a94b-451a-a6f2-6adf35f6164b (old id 407468)
date added to LUP
2016-04-01 11:34:16
date last changed
2021-01-06 01:03:05
@article{916101b6-a94b-451a-a6f2-6adf35f6164b,
  abstract     = {Thermal treatment of [OS3(CO)(12)] with diphenyl(2-thienyl)phosphane, Ph(2)p(C4H3S), results in the formation of [Os-3(CO)(12-x){Ph2P(C4H3S)}(x)] (x = 1-3, 1-3), but no C-H bond activation was observed. Reaction of [H2Os3(CO)(10)] with diphenyl(2-thienyl)phosphane at ambient temperature affords [HOs3(mu-H)(CO)(10){Ph2P(C4H3S}] (4), but when the same reaction is repeated at elevated temperatures, the cyclometallated species [(mu-H)Os-3(CO)(9){mu(3)-Ph(2)p(C4H2S)}] (5) and [mu-H) Os-3(CO)(8){mu 3-Ph2P(C4H2S)}(Ph2P(C4H3S)}] (6) are formed. In addition, two more products, tentatively assigned as [(mu-H)Os-3(CO)(6()mu(3)-Ph2P(C4H2S)}{mu-Ph2P(C4H3S)}{Ph2P-(C4H3S)}] (7) and [(mu-H)Os-3 (CO)(7) {mu-Ph2P(C4H2S)}] (4)tPh(2)P(C(4)H3(S)))(Ph2P(C4H3S))] (8) are obtained. The dynamic behaviours of 2, 5 and 6 have been studied by variable-temperature (VT) and H-1 P-31{H-1} NMR spectroscopy. The VT P-31{H-1} NMR spectra of [Os-3(CO)(10){Ph2P(C4H3S)}(2)] (2) demonstrate that a mixture of two isomers, which are in rapid exchange at room temperature, is present and that the less common cis-trans isomer, whose structure has been determined by X-ray crystallography, is favoured for this cluster. The VT H-1 NMR spectra of 5 indicate the presence of two isomers which are proposed to arise from an oscillation of the sigma,eta(2)-vinyl group of the thienyl moiety between two metal atoms. A similar fluxional process is proposed to occur in 6 and the assignment of the room-temperature structure(s) of this cluster was confirmed by H-1-Os-187 2D HMQC spectroscopy. In addition to 2, the solid-state structures of 3, 5 and 6 have been determined by X-ray crystallography. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006.},
  author       = {Kiriakidou-Kazemifar, Nitsa and Stchedroff, M and Mottalib, M A and Selva, S and Monari, M and Nordlander, Ebbe},
  issn         = {1099-0682},
  language     = {eng},
  number       = {10},
  pages        = {2058--2068},
  publisher    = {John Wiley and Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {Syntheses and fluxional processes of diphenyl(2-thienyl)phosphane derivatives of triosmium clusters},
  url          = {http://dx.doi.org/10.1002/ejic.200501141},
  doi          = {10.1002/ejic.200501141},
  year         = {2006},
}