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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

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)

Author

  • Kamal Hossain
  • Subas Rajbangshi
  • Ahibur Rahaman
  • Md Arshad H. Chowdhury
  • Tasneem A. Siddiquee
  • Shishir Ghosh
  • Michael G. Richmond
  • Ebbe Nordlander
  • Graeme Hogarth
  • Shariff E. Kabir

Summary, in English

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.

Department/s

  • Chemical Physics

Publishing year

2014

Language

English

Pages

231-239

Publication/Series

Journal of Organometallic Chemistry

Volume

760

Document type

Journal article

Publisher

Elsevier

Topic

  • Atom and Molecular Physics and Optics

Keywords

  • Triruthenium
  • Trifurylphosphine
  • Trithienylphosphine
  • Cyclometalation
  • Diphosphine
  • DFT

Status

Published

ISBN/ISSN/Other

  • ISSN: 0022-328X