Rhodium hydride complexes with phosphite / phosphito ligands: syntheses, reactions with isocyanates and the X-ray crystal structure of HRh{[P(OMe)2O]2H}2(PPh2Me)

Academic Article


  • The recently reported complex, HRh{[P(OMe)2O]2H}2(CO), is of interest because it contains both a metal hydride and an acidic proton. The carbonyl ligand in this complex is readily displaced by P-donor ligands. The bridging protons in the phosphite/phosphito ligands can be replaced by BF2 groups. These complexes do not react with carbon dioxide or carbon disulfide at room temperature and pressure, but the carbonyl complexes react with isocyanates to yield ureas and oligomers of the isocyanates. The major P-containing compound isolated from these reactions is [Rh{[P(OMe)2O]2H}3]. The reaction of HRh{[P(OMe)2O]2BF2}2(CO) with isocyanates gives a complex mixture of P-containing products in which cleavage of the POB bond has occurred. The X-ray crystal structure of HRh{[P(OMe)2O]2H}2(PPh2Me) is also reported. The complex crystallizes in the orthorhombic space group Pna21 (a 19.523(1), b 13.510(1), c 12.353(3) Å, V 3259.1 Å3, Z = 4). The complex exhibits a distorted octahedral structure with the Rh displaced out of the plane of the phosphite/phosphito ligands towards the PPh2Me ligand. The two phosphite/phosphito chelate rings in this complex are quite different with one planar and the other significantly distorted from a plane. This appears to be due to the different orientations of the phenyl groups of the PPh2Me ligand. © 1990.
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  • Varshney A; Gray GM
  • Start Page

  • 415
  • End Page

  • 429
  • Volume

  • 391
  • Issue

  • 3