Synthesis and Characterization of Square Planar Nickel(II)−Arylthiolate Complexes with the Biphenyl-2,2‘-dithiolate Ligand

Two new NiIIS4 complexes with the biphenyl-2,2‘-dithiolate ligand (L) are reported. The dinuclear complex 1,
[Ni2L3]2-, was formed in the reaction of 2−3 equiv of Na2L and [NiCl4]2- and the mononuclear complex [NiL2]2-
(2) by using 4−10 equiv of Na2L. Complexes 1 and 2 have been crystallographically characterized. (Et4N)2[1]·0.5S2Ph2, CH3CN:  C60H71N3Ni2S7, triclinic, P1̄, a = 13.806(2) Å, b = 14.267(2) Å, c = 16.873(2) Å, α =
69.263(10)°, β = 69.267(8)°, γ = 83.117(10)°, Z = 2, R1 = 0.0752 (wR2 = 0.2011). (Et4N)(Na·CH3CN)[2]: 
C34H39N2NaNiS4, triclinic, P1̄, a = 9.9570(10) Å, b = 13.2670(10) Å, c = 13.9560(10) Å, α = 108.489(7)°, β
= 90.396(6)°, γ = 103.570(4)°, Z = 2, R1 = 0.0390 (wR2 = 0.0995). Both complexes are square planar about
the nickel ion in the solid state as well as in solution. Most Ni(II)−thiolate complexes are square planar except
the tetrahedral mononuclear complexes with monodentate arylthiolate ligands that cannot force a square planar
geometry. The ligand (L) has some flexibility to change its bite angle via the phenyl−phenyl bond and should
not force a planar geometry on its complexes either. Therefore, it is interesting that 2 has adopted a square planar
structure. Complex 2 readily converts to 1 in solution when not in the presence of excess L in a process that is
presumably similar to that known for other mononuclear, bidentate ligated Ni(II) complexes. Both complexes, at
least in the solid state, appear to have an inclination to bind another metal ion on one face of the complex (Ni2+
in 1, Na+ in 2). We hope to take advantage of this in future work to synthesize relevant model complexes for the
active sites of the nickel−iron hydrogenases after suitable modifications are made to L.