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A comparative study of the reactivity of the lightly stabilized cluster [Os-3(CO)(8){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] towards tri(2-thienyl)-, tri(2-furyl)- and triphenyl-phosphine

Raha, Arun K.; Uddin, Md Nazim; Ghosh, Shishir; Miah, Abdur R.; Richmond, Michael G.; Tocher, Derek A.; Nordlander, Ebbe LU ; Hogarth, Graeme and Kabir, Shariff E. (2014) In Journal of Organometallic Chemistry 751. p.399-411
Abstract
Reactions of the lightly stabilized triosmium cluster [Os-3(CO)(8){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] with tri(2-thienyl)phosphine (PTh3) and tri(2-furyl)phosphine (PFu(3)) are described and compared to analogous reactions with PPh3. At room temperature, a number of products are isolated: [Os-3(CO)(10)(mu-dppm)] from CO addition, [Os-3(CO)(8)(PR3){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] from phosphine addition, [Os-3(CO)(9)(PR3)(mu-dppm)] from phosphine and CO addition and [Os-3(CO)(8)(PR3)(2)(mu-dppm)] from addition of two equivalents of phosphine. The latter are shown by NMR and X-ray diffraction to exist as 1,2-isomers, whereby one phosphine is bound to the non-dppm-substituted center and the second shares an osmium atom with one end of the... (More)
Reactions of the lightly stabilized triosmium cluster [Os-3(CO)(8){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] with tri(2-thienyl)phosphine (PTh3) and tri(2-furyl)phosphine (PFu(3)) are described and compared to analogous reactions with PPh3. At room temperature, a number of products are isolated: [Os-3(CO)(10)(mu-dppm)] from CO addition, [Os-3(CO)(8)(PR3){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] from phosphine addition, [Os-3(CO)(9)(PR3)(mu-dppm)] from phosphine and CO addition and [Os-3(CO)(8)(PR3)(2)(mu-dppm)] from addition of two equivalents of phosphine. The latter are shown by NMR and X-ray diffraction to exist as 1,2-isomers, whereby one phosphine is bound to the non-dppm-substituted center and the second shares an osmium atom with one end of the diphosphine. Heating 1,2-[Os-3(CO)(8)(PTh3)(2)(mu-dppm)] at 100 degrees C results in its clean isomerization to the 1,1-isomer in which both monodentate phosphines are located on the same osmium atom. Prolonged heating of [Os-3(CO)(8)(PR3)(2)(mu-dppm)] (R = Th, Ph) at 110 degrees C gives [Os-3(CO)(9)(PR3)(mu-dppm)] and the new lightly stabilized clusters [Os-3(CO)(7)(PR3){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)], the latter being formed by loss of phosphine and CO with concurrent metalation of a phenyl ring. Heating [Os-3(CO)(8)(PFu(3))(2)(mu-dppm)] at 110 degrees C gives [Os-3(CO)(9)(PFu(3))(mu-dppm)] together with the carbon-phosphorus bond cleavage products [Os-3(CO)(7)(mu-PFu(2))(mu(3)-eta(2)-C4H2O)(mu-H)(mu-dppm)] and [Os-3(CO)(7)(mu-PFu(2))(mu(3)-eta(2)-C6H3CH3)(mu-H)(mu-dppm)]. All new compounds were characterized by analytical and spectroscopic techniques together with single crystal X-ray diffraction analysis of nine clusters. Density functional theory (DFT) calculations have been carried out on isomers of [Os-3(CO)(8)(PR3)(2)(mu-dppm)] in order to understand the observed isomer ratios. (C) 2013 Elsevier B.V. All rights reserved. (Less)
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Contribution to journal
publication status
published
subject
keywords
Triosmium, Phosphines, Addition reactions, Isomerization, Carbon-phosphorus bond cleavage, DFT studies
in
Journal of Organometallic Chemistry
volume
751
pages
399 - 411
publisher
Elsevier
external identifiers
  • wos:000329864700036
  • scopus:84893784245
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2013.08.027
language
English
LU publication?
yes
id
dc934309-1bbc-435d-b50e-b94c21d580c8 (old id 4318576)
date added to LUP
2014-02-25 10:55:38
date last changed
2017-03-26 03:47:53
@article{dc934309-1bbc-435d-b50e-b94c21d580c8,
  abstract     = {Reactions of the lightly stabilized triosmium cluster [Os-3(CO)(8){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] with tri(2-thienyl)phosphine (PTh3) and tri(2-furyl)phosphine (PFu(3)) are described and compared to analogous reactions with PPh3. At room temperature, a number of products are isolated: [Os-3(CO)(10)(mu-dppm)] from CO addition, [Os-3(CO)(8)(PR3){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] from phosphine addition, [Os-3(CO)(9)(PR3)(mu-dppm)] from phosphine and CO addition and [Os-3(CO)(8)(PR3)(2)(mu-dppm)] from addition of two equivalents of phosphine. The latter are shown by NMR and X-ray diffraction to exist as 1,2-isomers, whereby one phosphine is bound to the non-dppm-substituted center and the second shares an osmium atom with one end of the diphosphine. Heating 1,2-[Os-3(CO)(8)(PTh3)(2)(mu-dppm)] at 100 degrees C results in its clean isomerization to the 1,1-isomer in which both monodentate phosphines are located on the same osmium atom. Prolonged heating of [Os-3(CO)(8)(PR3)(2)(mu-dppm)] (R = Th, Ph) at 110 degrees C gives [Os-3(CO)(9)(PR3)(mu-dppm)] and the new lightly stabilized clusters [Os-3(CO)(7)(PR3){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)], the latter being formed by loss of phosphine and CO with concurrent metalation of a phenyl ring. Heating [Os-3(CO)(8)(PFu(3))(2)(mu-dppm)] at 110 degrees C gives [Os-3(CO)(9)(PFu(3))(mu-dppm)] together with the carbon-phosphorus bond cleavage products [Os-3(CO)(7)(mu-PFu(2))(mu(3)-eta(2)-C4H2O)(mu-H)(mu-dppm)] and [Os-3(CO)(7)(mu-PFu(2))(mu(3)-eta(2)-C6H3CH3)(mu-H)(mu-dppm)]. All new compounds were characterized by analytical and spectroscopic techniques together with single crystal X-ray diffraction analysis of nine clusters. Density functional theory (DFT) calculations have been carried out on isomers of [Os-3(CO)(8)(PR3)(2)(mu-dppm)] in order to understand the observed isomer ratios. (C) 2013 Elsevier B.V. All rights reserved.},
  author       = {Raha, Arun K. and Uddin, Md Nazim and Ghosh, Shishir and Miah, Abdur R. and Richmond, Michael G. and Tocher, Derek A. and Nordlander, Ebbe and Hogarth, Graeme and Kabir, Shariff E.},
  issn         = {0022-328X},
  keyword      = {Triosmium,Phosphines,Addition reactions,Isomerization,Carbon-phosphorus bond cleavage,DFT studies},
  language     = {eng},
  pages        = {399--411},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {A comparative study of the reactivity of the lightly stabilized cluster [Os-3(CO)(8){mu(3)-Ph2PCH2P(Ph)C6H4}(mu-H)] towards tri(2-thienyl)-, tri(2-furyl)- and triphenyl-phosphine},
  url          = {http://dx.doi.org/10.1016/j.jorganchem.2013.08.027},
  volume       = {751},
  year         = {2014},
}