Jonathan R. Dilworth, D. Vaughan Griffiths, Suzanne J. Parrott and Yifan Zheng
The reaction of [Re2O3(S2CNEt2)4] with catechol in acetone yielded the dark orange complex [ReO{O(OH)C6H4}(S2CNEt 2)2] 1. The crystal structure shows a distorted-octahedral geometry with the oxo group trans to the monodentate catecholate ligand. The Re–O (catechol) bond length is typical of a Re–O single bond and implies little trans influence of the oxo ligand. Reaction of [Re2O3(S2CNEt2)4] with 1,4-dihydroxybenzene yielded the red-brown dimer [{ReO(S2CNEt2)2}2 (C6H4O2-1,4)] 2, in which the dianionic ligand bridges two rhenium centres. With 2-amino-4-methylphenol [ReO(OC6H3NH2-2-Me-4)(S2 CNEt2)2] 3 was obtained containing the ligand co-ordinated in a monodentate mode. Reaction of [Re2O3(S2CNEt2)4] with dithiolate proligands such as ethane-1,2-dithiol yielded [NEt2H2][ReOL2], L = C2H4S2-1,2 4, C6H4S2-1,2 5 or MeC6H3S2-3,4 6, where degradation of the dithiocarbamate ligands to form the diethylammonium counter ion occurs. Reaction of 1 with bidentate phosphines yielded green complexes of the general formula [Re(S2CNEt2)2L][BPh4], where L = Me2PCH2CH2PMe2 7 or Ph2PCH2CH2PPh2 8. These reactions can be contrasted to the inactivity of these phosphine ligands towards [Re2O3(S2CNEt2)4 ]. The reaction of [Re2O3(S2CNEt2)4] with the bidentate phosphinothiolate proligand PPh2(C6H4SH-2) in acetone at room temperature yielded the red-orange rhenium(III) complex [Re{PPh2(C6H4S-2)}2 (S2CNEt2)]·Me2CO 9. The crystal structure revealed a distorted-octahedral geometry. The sulfur donors of the phosphinothiolate ligands adopt a cis configuration. Reaction of [Re2O3(S2CNEt2)4] with the tridentate phosphinothiolate proligand PPh(C6H4SH-2)2 proceeded at room temperature to yield the red rhenium(V) complex [ReO{PPh(C6H4S-2)2}(S2 CNEt2)] 10. Its crystal structure shows a distorted-octahedral geometry. Reaction of [Re2O3(S2CNEt2)4] with SiMe3Cl yielded the new rhenium(V) precursor [ReCl2(S2CNEt2)2][BPh 4] 11 which permits investigation into rhenium dithiocarbamate chemistry without an oxo core.