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Synthesis of [Ru-3(CO)(9)(mu-dppf){P(C4H3E)(3)}] (E = O, S) and thermally induced cyclometalation to form [(mu-H)Ru-3(CO)(7)(mu-dppf){mu(3)-( C4H3E)(2)P(C4H2E)}] (dppf=1,1 '-bis(diphenylphosphino) ferrocene)

Hossain, Kamal LU ; Rajbangshi, Subas; Rahaman, Ahibur LU ; Chowdhury, Md Arshad H.; Siddiquee, Tasneem A.; Ghosh, Shishir; Richmond, Michael G.; Nordlander, Ebbe LU ; Hogarth, Graeme and Kabir, Shariff E. (2014) In Journal of Organometallic Chemistry 760. p.231-239
Abstract
The new clusters [Ru-3(CO)(9)(mu-dppf){P(C4H3E)(3)}] (1, E = O; 2, E = S) have been prepared from the Me3NO-induced decarbonylation of [Ru-3(CO)(10)(mu-dppf)] in the presence of PFu(3) (E = O) and PTh3 (E = S), respectively. Upon thermolysis in benzene, the major products are the cyclometalated clusters [(mu-H) Ru-3(CO)(7)(mu-dppf){mu(3)-(C4H3E)(2)P(C4H2E)}] (3, E - O; 4, E - S). This thermolytic behavior is in marked contrast to that previously noted for the analogous bis(diphenylphosphino) methane (dppm) complexes [Ru-3(CO)(9)(mu-dppm){P(C4H3E)(3)}], in which both carbon-hydrogen and carbon-phosphorus bond activation yields furyne- and thiophyne-capped clusters. The crystal structures of 1, 3 and 4 are presented and reveal that phosphine... (More)
The new clusters [Ru-3(CO)(9)(mu-dppf){P(C4H3E)(3)}] (1, E = O; 2, E = S) have been prepared from the Me3NO-induced decarbonylation of [Ru-3(CO)(10)(mu-dppf)] in the presence of PFu(3) (E = O) and PTh3 (E = S), respectively. Upon thermolysis in benzene, the major products are the cyclometalated clusters [(mu-H) Ru-3(CO)(7)(mu-dppf){mu(3)-(C4H3E)(2)P(C4H2E)}] (3, E - O; 4, E - S). This thermolytic behavior is in marked contrast to that previously noted for the analogous bis(diphenylphosphino) methane (dppm) complexes [Ru-3(CO)(9)(mu-dppm){P(C4H3E)(3)}], in which both carbon-hydrogen and carbon-phosphorus bond activation yields furyne- and thiophyne-capped clusters. The crystal structures of 1, 3 and 4 are presented and reveal that phosphine migration has occurred during the transformation of 1,2 into 3,4, respectively. The possible relation of the observed reactivity to the relative flexibilities of the diphosphine ligands is discussed. Density functional calculations have been performed on the model cluster [Ru-3(CO)(9)(mu-Me-4-dppf){ P(C4H3O)(3)]}], and these data are discussed relative to the ground-state energy differences extant between the different isomeric forms of this cluster. The dynamic NMR behavior displayed by the metalated thienyl ring in cluster 4 has also been investigated by computational methods, and the free energy of activation for the "windshield wiper" motion of the activated thienyl moiety determined. (C) 2013 Elsevier B.V. All rights reserved. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
Triruthenium, Trifurylphosphine, Trithienylphosphine, Cyclometalation, Diphosphine, DFT
in
Journal of Organometallic Chemistry
volume
760
pages
231 - 239
publisher
Elsevier
external identifiers
  • wos:000334295800031
  • scopus:84899450538
ISSN
0022-328X
DOI
10.1016/j.jorganchem.2013.09.021
language
English
LU publication?
yes
id
42900d61-44ef-4a19-b6d9-9290d31a91b8 (old id 4487809)
date added to LUP
2014-06-23 14:41:32
date last changed
2017-06-18 03:57:01
@article{42900d61-44ef-4a19-b6d9-9290d31a91b8,
  abstract     = {The new clusters [Ru-3(CO)(9)(mu-dppf){P(C4H3E)(3)}] (1, E = O; 2, E = S) have been prepared from the Me3NO-induced decarbonylation of [Ru-3(CO)(10)(mu-dppf)] in the presence of PFu(3) (E = O) and PTh3 (E = S), respectively. Upon thermolysis in benzene, the major products are the cyclometalated clusters [(mu-H) Ru-3(CO)(7)(mu-dppf){mu(3)-(C4H3E)(2)P(C4H2E)}] (3, E - O; 4, E - S). This thermolytic behavior is in marked contrast to that previously noted for the analogous bis(diphenylphosphino) methane (dppm) complexes [Ru-3(CO)(9)(mu-dppm){P(C4H3E)(3)}], in which both carbon-hydrogen and carbon-phosphorus bond activation yields furyne- and thiophyne-capped clusters. The crystal structures of 1, 3 and 4 are presented and reveal that phosphine migration has occurred during the transformation of 1,2 into 3,4, respectively. The possible relation of the observed reactivity to the relative flexibilities of the diphosphine ligands is discussed. Density functional calculations have been performed on the model cluster [Ru-3(CO)(9)(mu-Me-4-dppf){ P(C4H3O)(3)]}], and these data are discussed relative to the ground-state energy differences extant between the different isomeric forms of this cluster. The dynamic NMR behavior displayed by the metalated thienyl ring in cluster 4 has also been investigated by computational methods, and the free energy of activation for the "windshield wiper" motion of the activated thienyl moiety determined. (C) 2013 Elsevier B.V. All rights reserved.},
  author       = {Hossain, Kamal and Rajbangshi, Subas and Rahaman, Ahibur and Chowdhury, Md Arshad H. and Siddiquee, Tasneem A. and Ghosh, Shishir and Richmond, Michael G. and Nordlander, Ebbe and Hogarth, Graeme and Kabir, Shariff E.},
  issn         = {0022-328X},
  keyword      = {Triruthenium,Trifurylphosphine,Trithienylphosphine,Cyclometalation,Diphosphine,DFT},
  language     = {eng},
  pages        = {231--239},
  publisher    = {Elsevier},
  series       = {Journal of Organometallic Chemistry},
  title        = {Synthesis of [Ru-3(CO)(9)(mu-dppf){P(C4H3E)(3)}] (E = O, S) and thermally induced cyclometalation to form [(mu-H)Ru-3(CO)(7)(mu-dppf){mu(3)-( C4H3E)(2)P(C4H2E)}] (dppf=1,1 '-bis(diphenylphosphino) ferrocene)},
  url          = {http://dx.doi.org/10.1016/j.jorganchem.2013.09.021},
  volume       = {760},
  year         = {2014},
}