Preparation of a bis(hydrosulfido) complex of Mo having a tetraphosphine co-ligand and its transformation into MoRh2 and MoIr2 mixed-metal sulfido clusters

Dalton Trans. 2009 Aug 21:(31):6134-40. doi: 10.1039/b902386k. Epub 2009 Jun 4.

Abstract

The treatment of a Mo(0) complex with a tetraphosphine co-ligand [Mo(kappa(4)-P4)(Ph(2)PCH(2)CH(2)PPh(2))] (P4 = meso-o-C(6)H(4)(PPhCH(2)CH(2)PPh(2))(2)) with H(2)S gas in toluene at room temperature afforded [Mo(SH)(2)(kappa(4)-P4)] (1), which demonstrates the first Mo(II) bis(hydrosulfido) complex. Its trigonal-prismatic structure rarely observed for Mo(II) complexes has been determined by X-ray analysis. The reactions of 1 with [RhCl(CO)(2)](2) and [IrCl(CO)(2)(p-toluidine)] in the presence of NEt(3) resulted in the formation of the sulfido-bridged trinuclear clusters [Mo(kappa(4)-P4)(mu(3)-S)(2){Rh(CO)(2)}(2)] (4) and [Mo(kappa(4)-P4)(mu(3)-S)(2){Ir(CO)(2)}(2)] (5), respectively. The X-ray diffraction study has disclosed that the MoRh(2) cluster 4 in the solid state exists in two isomeric forms arising from the different orientation of P4 to the trigonal-prismatic Mo center, whereas the crystals of the Ir analogue 5 contains the molecules corresponding to only one of the two isomers observed for 4. The fluxional features of 1, 4, and 5 in solution have been confirmed by VT NMR studies.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Iridium / chemistry*
  • Ligands
  • Models, Molecular
  • Molecular Conformation
  • Molybdenum / chemistry*
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry
  • Phosphines / chemistry*
  • Rhodium / chemistry*
  • Sulfhydryl Compounds / chemistry*

Substances

  • Ligands
  • Organometallic Compounds
  • Phosphines
  • Sulfhydryl Compounds
  • Iridium
  • Molybdenum
  • Rhodium