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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

Triphenylphosphine-substituted selenido and sulfido clusters of osmium derived from Ph3P=Se or Ph3P=S

Author

  • H Akter
  • AJ Deeming
  • GMG Hossain
  • SE Kabir
  • DN Mondol
  • Ebbe Nordlander
  • A Sharmin
  • DA Tocher

Summary, in English

Cleavage of P=Se bonds occurs readily in the room-temperature treatment of [Os-3(CO) (10)(MeCN)(2)] with Ph3P=Se to give three new compounds, [Os-3(mu(3)-Se)(2)(CO)(8)(PPh3)] (2), [Os-3(mu(3)-Se)( mu(3)-CO)(CO)(7)(PPh3)(2)] (5) and [Os3(mu-OH)(2)(CO)(8)(PPh3)(2)] (6), respectively, and three known compounds, [Os-3(mu(3)-Se)(2)(CO)(9)] (1), [Os-3(mu(3)-Se)(mu-CO)(2)(CO)(7)(PPh3)] (3), and 1,2-[Os-3(CO)(10)(PPh3)(2)] (4). No evidence for any product containing a co-ordinated Ph3P--Se ligand was obtained. The analogous reaction between [OS3(CO)10(MeCN)2] and Ph3P=S produces five new compounds [Os-3(mu(3)-S)(2)(CO)(8)(PPh3)] (7), [Os-3(mu(3)-S)(mu-CO)(2)(CO)(7)(PPh3)] (8), [Os-3(mu(3)-S) (mu(3)- CO)(CO)(7)(PPh3)(2)] (9), [Os-3(mu(3)-)(2)(CO)(7)(PPh3)(2)] (11) and compound 6 in addition to the known compound 4. Treatment of with Me3NO at 50 degrees C gives the trinuclear cluster [Os-3(mu(3)-Se)(2)(CO)(7)(PPh3)(NMe3)] (13) and the hexanuclear cluster [Os-6(mu(3)-Se)(4)(CO)(14) (PPh3)(2)] (12). Treatment of compound 1 with PPh3 and Me3NO at room temperature gives [Os-3(mu(3)-Se)(2)(CO)(7)(PPh3)(2)] (10). Compound 2 reacts with PPh3 similarly to give 10. Compound 3 reacts with elemental selenium at 110 degrees C to give 2. The new compounds 2, 5, 6 and 8 were characterized by single-crystal X-ray diffraction. The compounds 3, 5, 8 and 9 contain Os-3(mu(3)-S) or Os-3(mu(3)-Se)cluster cores with three metal-metal bonds while 2, 7, 10, 11 and 12 contain Os-3(mu(3)-S)(2) or Os(mu(3)-Se)(2) cores two metal-metal bonds. The two hydroxy ligands in the triosmium cluster 6 bridging the open osmium-osmium edge and are probably derived from water. A study of the dynamic exchange of PPh3 ligands in 5 is also reported.

Department/s

  • Chemical Physics

Publishing year

2005

Language

English

Pages

4628-4639

Publication/Series

Journal of Organometallic Chemistry

Volume

690

Issue

21-22

Document type

Journal article

Publisher

Elsevier

Topic

  • Chemical Engineering

Keywords

  • triphenylphosphine selenide
  • triphenylphosphine sulfide
  • crystal structures
  • osmium carbonyl clusters

Status

Published

ISBN/ISSN/Other

  • ISSN: 0022-328X