Lewis acid enhanced axial ligation of [Mo2]4+ complexes.

We report here the syntheses, X-ray crystal structures, electrochemistry, and density functional theory (DFT) single-point calculations of three new complexes: tetrakis(monothiosuccinimidato)dimolybdenum(II) [Mo2(SNO5)4, 1a], tetrakis(6-thioxo-2-piperidinonato)dimolybdenum(II) [Mo2(SNO6)4, 1b], and chlorotetrakis(monothiosuccinimidato)pyridinelithiumdimolybdenum(II) [pyLiMo2(SNO5)4Cl, 2-py]. X-ray crystallography shows unusually short axial Mo2-Cl bond lengths in 2-py, 2.6533(6) Å, and dimeric 2-dim, 2.644(1) Å, which we propose result from an increased Lewis acidity of the Mo2 unit in the presence of the proximal Li(+) ion. When 2-py is dissolved in MeCN, the lithium reversibly dissociates, forming an equilibrium mixture of (MeCNLiMo2(SNO5)4Cl) (2-MeCN) and [Li(MeCN)4](+)[Mo2(SNO5)4Cl](-) (3). Cyclic voltammetry was used to determine the equilibrium lithium binding constant (room temperature, K(eq) = 95 ± 1). From analysis of the temperature dependence of the equilibrium constant, thermodynamic parameters for the formation of 2-MeCN from 3 (ΔH° = -6.96 ± 0.93 kJ mol(-1) and ΔS° = 13.9 ± 3.5 J mol(-1) K(-1)) were extracted. DFT calculations indicate that Li(+) affects the Mo-Cl bond length through polarization of metal-metal bonding/antibonding molecular orbitals when lithium and chloride are added to the dimolybdenum core.