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 Mo^VI 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)°.