Structural studies in the ruthenium(II)/(±)-ortho-Phenylenebis{methyl(phenyl)-phosphine/arsine} system. III. Crystal structures of Dichlorocarbonyl(dimethyl sulfoxide)-[ortho-phenylenebis {methyl(phenyl)phosphine}]ruthenium(II) and of cis-dicarbonyldichloro[(±)-ortho-phenylenebis{methyl(phenyl)arsine}]ruthenium(II)

Abstract

The crystal and molecular structure of the title complex, cis-[Ru(CO)Cl₂(dmso)(opmpp)] (1) (dmso ≡ dimethyl sulfoxide, Me₂SO; opmpp ≡ (±)-ortho-phenylenebis {methyl(phenyl)phosphine},[o-C₆H₄(PMePh)₂]), has been determined by a single-crystal X-ray diffraction study at 295(1) K, being refined to a residual of 0.050 for 6115 independent 'observed' reflections. Crystals are monoclinic, P2₁/c, a 11.180(7), b 12.957(6), c 17.567(9) Å, β 90.88(5)º, Z 4. The ruthenium-chlorine distances, trans to phosphine and carbonyl ligands, respectively, are 2.469(2), 2.446(2) Å; the ruthenium-phosphine distances, trans to the chloride and dimethyl sulfoxide ligands, respectively, are 2.292(1), 2.313(2) Å. Ruthenium-sulfur (dmso) is 2.380(2) Å, while the ruthenium-carbon(CO) is c. 1.72 Å. For cis-[Ru(CO)₂Cl₂(opmpa)] (2) (opmpa ≡ (±)-ortho-phenylenebis{methyl(phenyl)- arsine}, [o-C₆H₄(AsMePh)₂]), refinement led to a residual of 0.036 for 2423 independent 'observed' reflections. Crystals are monoclinic, P2₁/c, a 10.497(3), b 11.586(7), c 20.341(9) Å, β 105.31(4)º, Z 4. Ruthenium-arsine distances, trans to carbonyl and chlorine ligands, respectively, are 2.404(1), 2.455(1) Å. Ruthenium-chlorine distances, trans to arsine and carbonyl ligands, respectively, are 2.443(3), 2.433(2) Å, while ruthenium-carbon(CO) distances, trans to arsine and chlorine ligands, respectively, are 1 .920(8), 1 .872(8) Å.