TY - JOUR
T1 - Synthesis and characterization of metal (M =Al or Ga) 2-phosphino (phenolate/benzenethiolate) complexes and their electrochemical behavior in the presence of CO2
AU - Bruggen, Jessica A.
AU - Feller, Keyton D.
AU - Schickel, Henry I.
AU - Tuleushova, Nazym
AU - Zhukush, Medet
AU - Lam, Kevin
AU - Barry, Brian M.
AU - Kemp, Richard A.
PY - 2017/1/1
Y1 - 2017/1/1
N2 - 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.
AB - 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.
KW - Carbon dioxide
KW - Cyclic voltammetry
KW - Frustrated Lewis pair
KW - Main-group complex
KW - Phosphinobenzenethiolate
KW - Phosphinophenolate
KW - X-ray crystallography
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U2 - 10.3233/MGC-170245
DO - 10.3233/MGC-170245
M3 - Article
AN - SCOPUS:85037846651
VL - 16
SP - 307
EP - 319
JO - Main Group Chemistry
JF - Main Group Chemistry
SN - 1024-1221
IS - 4
ER -