Synthesis and crystal structure of complex compounds of oxyhalogenide Mo(V) and oxythiohalogenide Mo(VI) with triphenylphosphine oxide

Abstract

From a study of the interaction of MoSCl/sub 3/ with OP(C/sub 6/H/sub 5/)/sub 3/ (L) we established the conditions for synthesis and isolated complexes of composition (MoOCl/sub 3/L/sub 2/)-(Mo(O, Cl)/sub 2/Cl/sub 2/L/sub 2/) (I) and (MoO/sub 2/Cl/sub 2/L/sub 2/)(MoOSCl/sub 2/L/sub 2/) (II) in the form of single crystals. The crystals were monoclinic with almost identical unit cells but were different in color. It transpired that the structure of I agreed with that carried out in (1) and confirmed the heterovalent statistical distribution found by the authors for the Cl and O atoms occupying the two vertices of one of the two crystallographically independent Mo octahedra. Complex II is isostructural with I. The Mo atom is coordinated by two Cl atoms in trans positions, and by two O/sub L/ cis atoms. O and S are situated in trans positions to the two O/sub L/ atoms in Mo(1) whereas in Mo(2) octahedra these positions are occupied by two oxo atoms. Distances are Mo(2)-O/sub L/ 2.18(1) and 2.17(1) A, Mo(1)-O/sub L/ 2.10(2) and 2.16(1) A, Mo(2)=O 1.74 (2) and 1.77(1), Mo(1)=O 1.67 (1), Mo(1)=S 2.249(7), Mo(1)-Cl 2.396 (6) and 2.386(6), Mo(2)-Cl 2.394(6) and 2.378(6) A. The difference in the bond lengths Mo(1)-O/sub L/more » for the two L molecules is probably linked to the trans effect of the ligands.« less