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Abstract

A series of Group 13 complexes MLX₂ (M = Al or Ga, L = SC₆H₄-2-P ^t Bu₂ or OC₆H₄-2-P ^t Bu₂, X = Me or C₆F₅) have been synthesized and characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction. Reactions of Me₃Al or Me₃Ga with an equivalent of either 2- ^t Bu₂P(C₆H₄)OH (1) or 2- ^t Bu₂P(C₆H₄)SH (5) resulted in the formation of four new (2,3,6, and 7), 4-coordinate dimethyl chelate (S,P or O,P) complexes via methane elimination. The dimethyl gallium complexes (3 and 7) underwent a further reaction with excess B(C₆F₅)₃, and through ligand exchange (methyl/pentafluorophenyl), resulted in the disubstituted bis(pentafluorophenyl) analogs (4 and 8). Cyclic voltammetry (CV) experiments for all compounds in the presence of and the absence of (1–8) CO₂ were performed. For compounds showing cathodic reduction waves under CO₂ (2,3,4, and 6), bulk electrolysis experiments were performed. Electrochemical studies indicate that, for several compounds, a transient CO₂ adduct is formed which undergoes a one-electron, irreversible (or partially irreversible) reduction to form an unstable radical anion.

Keywords

Carbon dioxide main-group complex cyclic voltammetry X-ray crystallography phosphinophenolate phosphinobenzenethiolate frustrated Lewis pair

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Synthesis and characterization of metal (M = Al or Ga) 2-phosphino(phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO 2

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