The structure of dinitrosylbis(triphenylphosphine)rhodium perchlorate, [Rh(NO)2(P(C6H5)3)2] [CIO4], has been determined from three-dimensional X-ray data collected by counter methods. The compound crystallizes in the space group C2/c of the monoclinic system with four molecules in a unit cell of dimensions a = 17.134 (4) Å, b = 12.327 (3) Å, c = 17.166 (4) Å, and β = 108.17 (2)°. The observed and calculated densities are 1.55 (3) and 1.52 g cm-3, respectively. Least-squares refinement of the structure has led to a value of the conventional R index (on F) of 0.061 for the 4649 independent reflections having Fo2> 3σ (Fo2). The crystal structure consists of well-separated, discrete, monomeric ions. The coordination geometry around the rhodium atom is best described as intermediate between tetrahedral and square planar; N-Rh-N = 157.5 (3) and P-Rh-P = 115.88(5)°. The Rh-N-O angle is 158.9 (4)°. The dihedral angle between the N-Rh-N and P-Rh-P planes is 86.0 (1)°, The structure is compared with those of other isoelectronic M(NO)2(PPh3)2 complexes, and trends in structure and activity as catalysts for the reaction 2NO + CO ⟶ N2O + CO2 are correlated.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry