BIS-PHENYLNITRENE COMPLEX OF MOLYBDENUM WITH A BENT NITRENE LIGAND - PREPARATION AND STRUCTURE OF CIS-MO(NC6H5)2(S2CN(C2H5)2)2

The first bisnitrene complex of molybdenum, Mo(NC6H5)2(S2CN(C2H5)2)2, has been prepared in high yield by allowing an excess of phenyl azide to react with Mo(CO)2(S2CN(C2H5)2)2in dry methylene chloride. Red-brown, solvent-free crystals of the complex were grown from methylene chloride-hexane. The structure of the complex was determined at-130 °C using X-ray diffraction techniques. The complex is monomeric and six coordinate with a somewhat distorted octahedral geometry caused by the small bite angles of the sulfur chelates, 67.60 (5) and 69.51 (4)° the angle between the nitrene ligands is 103.5 (2)°. of special import are the inequivalent phenylnitrene ligands. One nitrene is strongly bent at the nitrogen atom with Mo-N(1)-C(1) = 139.4 (4)° and Mo-N(1) = 1.789 (4) Å, and the other nitrene is nearly linear and has a shorter metal-nitrogen distance with Mo-N(3)-C(l7) = 169.4 (4)° and Mo-N(3) = 1.754 (4) Å. Available structural evidence indicates that linear nitrene ligands exert little if any trans influence on trans ligands while the bent nitrene in the title complex has a significant trans influence. The Mo-S(4) distance of the sulfur atom trans to N(l) is 0.15 Å longer than that which is trans to N(3), and 0.30 Å longer than that which is trans to another sulfur. The title complex crystallizes in space group P21/n with a = 17.193(8) Å, b = 10.194 (4) Å, c = 18.127 (8) Å, β = 123.59 (i)°, and Z = 4. On the basis of 3518 unique reflections with FO2> 3σ(FO2), the structure was refined using full-matrix, least-squares methods to R(F)= 0.042 and RW(F) = 0.055. © 1979, American Chemical Society. All rights reserved.