Replacement of imido by disulfido at the molybdenum(VI) centre: reactivity of bis(imido) complexes [Mo(η 2-S 2CNEt 2) 2(NR) 2] with hydrogen sulfide and Lawesson's reagent: X-ray crystal structure of [Mo(η 2-S 2CNEt 2) 2(η 2-S 2)( N-2,6-Cl 2C 6H 3)

Abstract

Reactions of molybdenum(VI) bis(imido) complexes [Mo(η 2-S 2CNEt 2) 2(NR) 2] with hydrogen sulfide and Lawesson's reagent, [PS(4-MeOC 6H 4)(μ-S)] 2, have been carried out in an attempt to generate imido–sulfido complexes [Mo(η 2-S 2CNEt 2) 2(NR)(S)], however, while in all cases one imido ligand is lost, imido–disulfido complexes [Mo(η 2-S 2CNEt 2) 2(η 2-S 2)(NR)] are the major products and [Mo(η 2-S 2CNEt 2) 2(η 2-S 2)( N-2,6-Cl 2C 6H 3)] has been characterised crystallographically. The ligands are arranged in a distorted pentagonal bipyramidal configuration with the imido ligand occupying an axial site being characterised by a short MoN bond of 1.747(8) Å and a MoNC( ipso) angle of 164.9(8)°. The disulfido ligand occupies two equatorial sites with a SS bond length of 2.034(5) Å.