The reactions of dinitrogen complexes of molybdenum with thiols and sulphenyl halides

Abstract

The dinitrogen complex trans-[Mo(N₂)₂dpe)₂](dpe = Ph₂PCH₂CH₂PPh₂) reacts with thiols RSH (R = Et, Prⁿ, Buⁿ, or Ph) in tetrahydrofuran (thf) to give the diamagnetic complexes [Mo(SR)₂(dpe)₂], together with dihydrogen and two mole equivalents of dinitrogen. trans-[Mo(N₂)₂(depe)₂](depe = Et₂PCH₂CH₂PEt₂) gives [Mo(SPh)₂(depe)₂] with thiophenol. With PhSCl, trans-[Mo(N₂)₂(dpe)₂] gives [MoCl(SPh)(dpe)₂] and 2N₂, but with an excess of PhSBr, [MoBr₂(dpe)₂]Br₃ results. The dithio-complexes act as bidentate sulphur-donor ligands and the paramagnetic thio-bridged binuclear complexes [(dpe)₂Mo(SR)₂MoCl₄] and [(dpe)₂Mo(SBuⁿ)₂MoCl₃(thf)]Cl (R = Ph, Et, Prⁿ, and Buⁿ) have been prepared, whose magnetic moments indicate bond formation between molybdenum atoms. The diamagnetic adduct [(dpe)₂Mo(SBuⁿ)₂Mo(CO)₄] has also been obtained.