Ruthenium(II) carbonyl complexes containing tertiary phosphine chalcogenide ligands of the type Ph3PX; X=O, S, Se

Pratap Chutia, Nandini Kumari, Manab Sharma, John Derek Woollins, Alexandra Martha Zoya Slawin, Dipak K Dutta

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

The reactions of polymeric complex [Ru(CO)(2)Cl-2](n) with triphenyl phosphine chalcogenide ligands Ph3PX; X = O(a), S(b), Se(c) in 1:1 (Ru:L ratio) molar ratio gives five-coordinate complexes of the type [Ru(CO)(2)Cl-2(Ph3PX)](1a-c) while 1:2 (Ru:2L ratio) molar ratio produces six-coordinate [RU(CO)(2)Cl-2(Ph3PX)(2)](2a-c) complexes. The complexes 1a-c and 2a-c exhibit two equally intense nu(CO) bands in the range 2059-1989 and 2050-1980 cm(-1), respectively, indicating cis-disposition of the two terminal carbonyl groups. The values of nu(CO) frequencies irrespective of the complexes, in general, follow the order: Ph3PO > Ph3PS > Ph3PSe which may be ascribed in terms of "Soft-Hard" (Ru(II)-O) and "Soft-Soft" (Ru(II)-S/Se) interactions. The nu(PX) bands of the complexes observed in the range 1173-538 cm(-1) are 19-41 cm(-1) lower than those of the corresponding free ligands indicating the formation of Ru-X bonds. The molecular structure of the complex [Ru(CO)(2)Cl-2(Ph3PS)(2)] was determined by single X-ray crystallography. The crystal is monoclinic, space group Cc; a = 11.4990 Angstrom. b = 17.3966 Angstrom, c = 18.4788 Angstrom; alpha = 90degrees, beta = 98.160degrees, 90degrees. In the molecule, the Ru(II) atom occupies the center of a slightly distorted octahedral geometry which consists of two trans-S atoms of two Ph3PS ligands, two cis-CO groups and two cis-chlorides. The complexes have also been characterized by elemental analysis, H-1, C-13 and P-31 NMR spectroscopy. (C) 2004 Elsevier Ltd. All rights reserved.

Original languageEnglish
Pages (from-to)1657-1661
Number of pages5
JournalPolyhedron
Volume23
Issue number9
DOIs
Publication statusPublished - 27 May 2004

Keywords

  • ruthenium(II) carbonyl complexes
  • tertiary phosphine chalcogenides
  • "Soft-Hard" and "Soft-Soft" interactions
  • X-ray crystal structure
  • octahedral structure
  • CATALYTIC-ACTIVITY
  • CATIONIC RHODIUM(I)
  • METAL CARBONYLS
  • TRIPHENYLPHOSPHINE
  • METHANOL
  • RU(CO)2L2X2
  • SULFIDES
  • ISOMERS
  • OXIDES

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