Structural diversity in a family of copper(I) thioether complexes

Article abstract of DOI:10.1021/ic010273a

Copper(I) complexes of the tridentate thioether ligands [PhB(CH₂SCH₃)₃] (abbreviated PhTt), [PhB(CH₂SPh)₃] (PhTt^Ph), [PhB(CH₂S^tBu)₃] (PhTt^tBu), and [PhB(CH₂S^PTol)₃] (PhTt^pTol) and bidentate thioether ligands [Ph₂B(CH₂SCH₃)₂] (Ph₂Bt), [Et₂B(CH₂SCH₃)₂] (Et₂Bt), and [Ph₂B(CH₂SPh)₂] (Ph₂Bt^Ph) have been prepared and characterized. The solution and solid state structures are highly sensitive to the identity of the borato ligand employed. Ligands possessing the smaller (methylthio)methyl donors, [PhTt] and [Ph₂Bt], yielded tetrameric species, [(PhTt)Cu]₄ and [(Ph₂Bt)Cu]₄, containing both terminal and bridging thioether ligation. The ligands containing the larger (arylthio)methyl groups, [PhTt^Ph] and [PhTt^pTol], form monomeric [PhTt^Ar]Cu(NCCH₃) in solution and one-dimensional extended structures in the solid state. Each complex type reacted cleanly with acetonitrile, pyridine, or triphenylphosphine generating the corresponding four-coordinate monomer, of which [PhTt^Ph]Cu(PPh₃), [PhTt^pTol]Cu(PPh₃), and [Et₂Bt]Cu(PPh₃)₂ have been structurally characterized.