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Synthesis, Characterization, and Novel Fluxional Mechanisms of Triosmium Clusters Containing the Highly Flexible Ligand Ph2PC2H4SC2H4SC2H4PPh2 (PSSP)

Persson, Roger LU ; Stchedroff, Marc; Uebersezig, Bettina; Gobetto, Roberto; Steed, Jonathan W.; Prince, Paul D.; Monari, Magda and Nordlander, Ebbe LU (2010) In Organometallics 29(10). p.2223-2233
Abstract
Treatment of Ph2PC2H4SC2H4SC2H4PPh2 (PSSP) with [Os-3(CO)(11)(NCMe)] under mild conditions yields [{Os-3(CO)(11)}(2)(mu-PSSP)], 1, and [Os-3(CO)(11)(PSSP)], 2. In cluster 1 the ligand links two trinuelear cluster subunits, coordinating via its phosphine moieties. In cluster 2, the ligand is coordinated through one of the phosphine groups, while the remaining part of the PSSP ligand is oriented in a dangling mode. Treatment of [Os-3(CO)(11)(NCMe)(2)] with PSSP yields 1,2-[Os-3(CO)(10)(PSSP)], 3. NMR data presented in this paper indicate that a concerted cis/trans isomerism with respect to the phosphines operates in the cluster. This type of process has not been observed previously for a bridging ligand, but has been detected in the case of... (More)
Treatment of Ph2PC2H4SC2H4SC2H4PPh2 (PSSP) with [Os-3(CO)(11)(NCMe)] under mild conditions yields [{Os-3(CO)(11)}(2)(mu-PSSP)], 1, and [Os-3(CO)(11)(PSSP)], 2. In cluster 1 the ligand links two trinuelear cluster subunits, coordinating via its phosphine moieties. In cluster 2, the ligand is coordinated through one of the phosphine groups, while the remaining part of the PSSP ligand is oriented in a dangling mode. Treatment of [Os-3(CO)(11)(NCMe)(2)] with PSSP yields 1,2-[Os-3(CO)(10)(PSSP)], 3. NMR data presented in this paper indicate that a concerted cis/trans isomerism with respect to the phosphines operates in the cluster. This type of process has not been observed previously for a bridging ligand, but has been detected in the case of corresponding triosmium clusters with bis-monodentate phosphine ligands. Oxidative decarbonylation of [{Os-3(CO)(11)}(2)(mu-PSSP)], 1, with Me3NO yields cluster [{Os-3(CO)(10)}(2)(mu-PSSP)], 4. This cluster consists of two P,S-bridged cluster units. In solution at room temperature, 4 undergoes a slow rearrangement from a 1,2-bridging to a 1,1-chelating coordination mode. The crystal structures of clusters 1, 3, and 4 are reported. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Organometallics
volume
29
issue
10
pages
2223 - 2233
publisher
The American Chemical Society
external identifiers
  • wos:000277597500005
  • scopus:77952400666
ISSN
1520-6041
DOI
10.1021/om900966c
language
English
LU publication?
yes
id
a019dca2-ffc7-4ea1-94d8-c24bc8bbf359 (old id 1617734)
date added to LUP
2010-06-23 14:09:39
date last changed
2018-05-29 11:22:01
@article{a019dca2-ffc7-4ea1-94d8-c24bc8bbf359,
  abstract     = {Treatment of Ph2PC2H4SC2H4SC2H4PPh2 (PSSP) with [Os-3(CO)(11)(NCMe)] under mild conditions yields [{Os-3(CO)(11)}(2)(mu-PSSP)], 1, and [Os-3(CO)(11)(PSSP)], 2. In cluster 1 the ligand links two trinuelear cluster subunits, coordinating via its phosphine moieties. In cluster 2, the ligand is coordinated through one of the phosphine groups, while the remaining part of the PSSP ligand is oriented in a dangling mode. Treatment of [Os-3(CO)(11)(NCMe)(2)] with PSSP yields 1,2-[Os-3(CO)(10)(PSSP)], 3. NMR data presented in this paper indicate that a concerted cis/trans isomerism with respect to the phosphines operates in the cluster. This type of process has not been observed previously for a bridging ligand, but has been detected in the case of corresponding triosmium clusters with bis-monodentate phosphine ligands. Oxidative decarbonylation of [{Os-3(CO)(11)}(2)(mu-PSSP)], 1, with Me3NO yields cluster [{Os-3(CO)(10)}(2)(mu-PSSP)], 4. This cluster consists of two P,S-bridged cluster units. In solution at room temperature, 4 undergoes a slow rearrangement from a 1,2-bridging to a 1,1-chelating coordination mode. The crystal structures of clusters 1, 3, and 4 are reported.},
  author       = {Persson, Roger and Stchedroff, Marc and Uebersezig, Bettina and Gobetto, Roberto and Steed, Jonathan W. and Prince, Paul D. and Monari, Magda and Nordlander, Ebbe},
  issn         = {1520-6041},
  language     = {eng},
  number       = {10},
  pages        = {2223--2233},
  publisher    = {The American Chemical Society},
  series       = {Organometallics},
  title        = {Synthesis, Characterization, and Novel Fluxional Mechanisms of Triosmium Clusters Containing the Highly Flexible Ligand Ph2PC2H4SC2H4SC2H4PPh2 (PSSP)},
  url          = {http://dx.doi.org/10.1021/om900966c},
  volume       = {29},
  year         = {2010},
}