A convenient route to complexes of the type [MoO(SR)4]–(R = aryl) and [MoO{S(CH2)nS}2]–(n= 2 or 3) preparation and crystal structure of [PPh4][Mo(NNMe2)O(SC6H5)3]·(C2H5)2O
Abstract
The complexes [MoO(SR)4]–(R = aryl) and [MoO{S(CH2)nS}2]–(n= 2 or 3) can be prepared by reaction of an MoVI butanediolato-complex with thiolate anion in methanol. The complexes [MoO(SPh)4]– react with R′2NNH2[R′2= Me2 or (CH2)5] in refluxing CH3CN to give [Mo(NNR′2)O(SPh)3]–. Crystal Data for [PPh4][Mo(NNMe2)O(SC6H5)3]·(C2H5)2O : space group Pbca, a= 12.789(4), b= 19.375(3), c= 36.941(3)Å, Z= 8.3 225 Independent reflections with I > 3σ(I) gave R= 0.076. The geometry is essentially square-pyramidal with an apical oxo-group and the NNMe2 group in the basal plane. Although the MO–N and N–N distances of 1.821(9) and 1.292(14)Å respectively are analogous to other hydrazido(2–) complexes, the Mo–N–NMe2 system is anomalously bent with MO–N–N = 152.5(10)°.