Synthesis and characterization of metal (M =Al or Ga) 2-phosphino (phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO2

Jessica A. Bruggen, Keyton D. Feller, Henry I. Schickel, Nazym Tuleushova, Medet Zhukush, Kevin Lam, Brian M. Barry, Richard A. Kemp

Research output: Contribution to journalArticlepeer-review

Abstract

series of Group 13 complexes MLX2 (M=Al or Ga, L=SC6H4-2-PtBu2 or OC6H4-2-PtBu2, X=Me or C6F5) have been synthesized and characterized by multinuclearNMRspectroscopy and single crystal X-ray diffraction. Reactions of Me3Al or Me3Ga with an equivalent of either 2-tBu2P(C6H4)OH (1) or 2-tBu2P(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.

Original languageEnglish
Pages (from-to)307-319
Number of pages13
JournalMain Group Chemistry
Volume16
Issue number4
DOIs
Publication statusPublished - Jan 1 2017

Keywords

  • Carbon dioxide
  • Cyclic voltammetry
  • Frustrated Lewis pair
  • Main-group complex
  • Phosphinobenzenethiolate
  • Phosphinophenolate
  • X-ray crystallography

ASJC Scopus subject areas

  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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