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Synthesis and Characterization of Triosmium Clusters Containing the Bidentate Ligand Ph2PCH2CH2SMe; Detection of an Unusual Isomerisation Reaction

Persson, Roger; Monari, Magda; Gobetto, Roberto; Russo, Andrea; Aime, Silvio; Calhorda, Maria and Nordlander, Ebbe LU (2001) In Organometallics 20(20). p.4150-4160
Abstract
Diphenylphosphinoethylene methyl sulfide, Ph2PCH2CH2SMe, reacts with [Os3(CO)11(NCMe)] yielding [Os3(CO)11(Ph2PCH2CH2SMe)]. Treatment of [Os3(CO)10(NCMe)2] with 1 equiv of the P,S ligand initially yields the cluster 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)], in which the phosphine and the thioether moieties coordinate to different metal atoms of the metal triangle; addition of two or more equivalents of the ligand yields 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)] and [Os3(CO)10(Ph2PCH2CH2SMe)2]. The cluster 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)] is metastable and undergoes a slow isomerization reaction at room temperature to form 1,1-[Os3(CO)10(Ph2PCH2CH2SMe)], in which the ligand chelates one Os atom. Computational modeling of 1,2- and 1,1-[Os3(CO)10(Ph2PCH2CH2SMe)]... (More)
Diphenylphosphinoethylene methyl sulfide, Ph2PCH2CH2SMe, reacts with [Os3(CO)11(NCMe)] yielding [Os3(CO)11(Ph2PCH2CH2SMe)]. Treatment of [Os3(CO)10(NCMe)2] with 1 equiv of the P,S ligand initially yields the cluster 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)], in which the phosphine and the thioether moieties coordinate to different metal atoms of the metal triangle; addition of two or more equivalents of the ligand yields 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)] and [Os3(CO)10(Ph2PCH2CH2SMe)2]. The cluster 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)] is metastable and undergoes a slow isomerization reaction at room temperature to form 1,1-[Os3(CO)10(Ph2PCH2CH2SMe)], in which the ligand chelates one Os atom. Computational modeling of 1,2- and 1,1-[Os3(CO)10(Ph2PCH2CH2SMe)] indicates that the two clusters are of similar stability, with the latter isomer being of slightly lower energy. The dynamic behavior of the clusters have been investigated by variable-temperature 13C{1H} and 31P{1H} NMR, and the kinetics of the isomerization reaction have been measured. The latter indicate that the isomerization proceeds via an associative mechanism which is proposed to involve an intramolecular nucleophilic attack by the coordinated sulfur on an osmium atom. The solid state structures of [Os3(CO)11(Ph2PCH2CH2SMe)], 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)], and 1,1-[Os3(CO)10(Ph2PCH2CH2SMe)] are reported. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
20
issue
20
pages
4150 - 4160
publisher
The American Chemical Society
external identifiers
  • scopus:0035497141
ISSN
1520-6041
DOI
10.1021/om010223d
language
English
LU publication?
yes
id
14764897-b4af-4da3-835f-7214128f1457 (old id 959545)
date added to LUP
2008-08-18 12:26:02
date last changed
2018-01-07 06:00:46
@article{14764897-b4af-4da3-835f-7214128f1457,
  abstract     = {Diphenylphosphinoethylene methyl sulfide, Ph2PCH2CH2SMe, reacts with [Os3(CO)11(NCMe)] yielding [Os3(CO)11(Ph2PCH2CH2SMe)]. Treatment of [Os3(CO)10(NCMe)2] with 1 equiv of the P,S ligand initially yields the cluster 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)], in which the phosphine and the thioether moieties coordinate to different metal atoms of the metal triangle; addition of two or more equivalents of the ligand yields 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)] and [Os3(CO)10(Ph2PCH2CH2SMe)2]. The cluster 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)] is metastable and undergoes a slow isomerization reaction at room temperature to form 1,1-[Os3(CO)10(Ph2PCH2CH2SMe)], in which the ligand chelates one Os atom. Computational modeling of 1,2- and 1,1-[Os3(CO)10(Ph2PCH2CH2SMe)] indicates that the two clusters are of similar stability, with the latter isomer being of slightly lower energy. The dynamic behavior of the clusters have been investigated by variable-temperature 13C{1H} and 31P{1H} NMR, and the kinetics of the isomerization reaction have been measured. The latter indicate that the isomerization proceeds via an associative mechanism which is proposed to involve an intramolecular nucleophilic attack by the coordinated sulfur on an osmium atom. The solid state structures of [Os3(CO)11(Ph2PCH2CH2SMe)], 1,2-[Os3(CO)10(-Ph2PCH2CH2SMe)], and 1,1-[Os3(CO)10(Ph2PCH2CH2SMe)] are reported.},
  author       = {Persson, Roger and Monari, Magda and Gobetto, Roberto and Russo, Andrea and Aime, Silvio and Calhorda, Maria and Nordlander, Ebbe},
  issn         = {1520-6041},
  language     = {eng},
  number       = {20},
  pages        = {4150--4160},
  publisher    = {The American Chemical Society},
  series       = {Organometallics},
  title        = {Synthesis and Characterization of Triosmium Clusters Containing the Bidentate Ligand Ph2PCH2CH2SMe; Detection of an Unusual Isomerisation Reaction},
  url          = {http://dx.doi.org/10.1021/om010223d},
  volume       = {20},
  year         = {2001},
}