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)(η1-C6H4OCH3-4-CH2S) and ReO(η3-SCH2C5H3NCH2S)(η1-C5H4NH-2-S)Cl

摘要

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, P1, 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) ų, Z=4. For >16, C₁₃H₁₁ClNO₂S₂Re: orthorhombic, P2₁2₁2₁, a=6.9728(6), b=13.477(1), c=15.761(1) Å, V=1481.1(2) ų, 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) ų, 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) ų, 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) ų, Z=8.