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.