Synthesis and characterization of oxorhenium(V)–‘3+1’ mixed thiolate [SNS]/[S] and [ONS]/[S] complexes. Crystal and molecular structures of [ReO(η3-SCH2C5H3NCH2S)(η1-C6H4Br-4-S)], [ReO(η3-SCH2C5H3NCH2O)(η1-C6H4X-4-S)] (X=Cl, OMe), [ReO(η3-SCH2C5H3NCH2O)(η

The reaction of [ReOCl3(PPh3)2] with the tridentate ligands 2,6-dithiomethylpyridine (4) or 6-thiomethyl-2-pyridinemethanol (5) and the appropriate monothiols, such as para-substituted benzenethiols (C6H4X-4-SH) (where X=F, Cl, Br and OCH3) and para-substituted benzylmercaptans (C6H4X-4-CH2SH) (where X=F, Cl and OCH3) in the presence of Et3N leads to the isolation of a series of integrated ‘3+1’ oxorhenium(V) complexes. Similarly, reaction of [ReOCl3(PPh3)2] with 2-mercaptopyridine and 4 afforded a cationic oxorhenium(V) complex, [ReO(η3-SCH2C5H3NCH2S)(η1-C5H4NH-2-S)][Cl] (22). Crystal data for 10, C13H11BrNOS3Re: triclinic, P1̄, a=7.2909(5), b=14.1978(9), c=15.991(1) Å, α=77.184(1), β=86.588(1), γ=75.507(1)°, V=1562.69(18) Å3, Z=4. For 16, C13H11ClNO2S2Re: orthorhombic, P212121, a=6.9728(6), b=13.477(1), c=15.761(1) Å, V=1481.1(2) Å3, Z=4. For 18, C14H14NO3S2Re: monoclinic, P21/c, a=15.6512(14), b=7.6678(7), c=13.732(1) Å, β=112.489(1)°, V=1522.7(2) Å3, Z=4. For 21, C15H16NO3S2Re: monoclinic, P21/c, a=13.929(1), b=7.741(1), c=15.583(2) Å, β=103.600(2)°, V=1633.1(3) Å3, Z=4. For 22, C12H11ClN2OS3Re: monoclinic, C21/c, a=27.827(3), b=8.529(1), c=14.957(2) Å, β=119.314(2)°, V=3095.3(6) Å3, Z=8.