Synthesis and characterization of oxorhenium(V)-'3+1' mixed thiolate [SNS]/[S] and [ONS]/[S] complexes. Crystal and molecular structures of [ReO(eta-SCH(2)C(5)H(3)NCH(2)S)(eta-C(6)H(4)Br-4-S)], [ReO(eta-SCH(2)C(5)H(3)NCH(2)O)(eta-C(6)H(4)X-4-S)] (X=Cl, OMe), [ReO(eta-SCH(2)C(5)H(3)NCH(2)O)(eta-C(6)H(4)OCH(3)-4-CH(2)S)] and [ReO(eta-SCH(2)C(5)H(3)NCH(2)S)(eta-C(5)H(4)NH-2-S)][Cl].

The reaction of [ReOCl(3)(PPh(3))(2)] with the tridentate ligands 2,6-dithiomethylpyridine (4) or 6-thiomethyl-2-pyridinemethanol (5) and the appropriate monothiols, such as para-substituted benzenethiols (C(6)H(4)X-4-SH) (where X=F, Cl, Br and OCH(3)) and para-substituted benzylmercaptans (C(6)H(4)X-4-CH(2)SH) (where X=F, Cl and OCH(3)) in the presence of Et(3)N leads to the isolation of a series of integrated '3+1' oxorhenium(V) complexes. Similarly, reaction of [ReOCl(3)(PPh(3))(2)] with 2-mercaptopyridine and 4 afforded a cationic oxorhenium(V) complex, [ReO(eta(3)-SCH(2)C(5)H(3)NCH(2)S)(eta(1)-C(5)H(4)NH-2-S)][Cl] (22). Crystal data for 10, C(13)H(11)BrNOS(3)Re: triclinic, P1, a=7.2909(5), b=14.1978(9), c=15.991(1) A, alpha=77.184(1), beta=86.588(1), gamma=75.507(1) degrees , V=1562.69(18) A(3), Z=4. For 16, C(13)H(11)ClNO(2)S(2)Re: orthorhombic, P2(1)2(1)2(1), a=6.9728(6), b=13.477(1), c=15.761(1) A, V=1481.1(2) A(3), Z=4. For 18, C(14)H(14)NO(3)S(2)Re: monoclinic, P2(1)/c, a=15.6512(14), b=7.6678(7), c=13.732(1) A, beta=112.489(1) degrees , V=1522.7(2) A(3), Z=4. For 21, C(15)H(16)NO(3)S(2)Re: monoclinic, P2(1)/c, a=13.929(1), b=7.741(1), c=15.583(2) A, beta=103.600(2) degrees , V=1633.1(3) A(3), Z=4. For 22, C(12)H(11)ClN(2)OS(3)Re: monoclinic, C2(1)/(c), a=27.827(3), b=8.529(1), c=14.957(2) A, beta=119.314(2) degrees , V=3095.3(6) A(3), Z=8.