Unusual Coordination Chemistry of Organoaluminum and -gallium Complexes in N2S and NS Coordination Environments. Synthesis and Crystal Structure of (Me2Al)[NC5H4CMeNNC(S)NC3H7](AlMe2) and (Me2Ga)[PhMeCNNC(S)NPh](GaMe2)

The synthesis and characterization of the dinuclear group 13 heterocyclic carboxaldehyde thiosemicarbazone complexes (Me 2 M)[NC 5 H 4 CMeNNC(S)NR](MMe 2 ) (M = Al, R = Me ( 1 ), i C 3 H 7 ( 3 ), Ph ( 5 ); M = Ga, R = Me ( 2 ), i C 3 H 7 ( 4 ), Ph (6)) and acetophenone thiosemicarbazone complexes (Me 2 M)(CH 3 RCNNC(S)NR‘)(MMe 2 ) (M = Al, R = Ph, R‘ = Ph ( 7 ); M = Al, R = CH 3, R‘ = CH 3 ( 9 ); M = Ga, R = Ph, R‘ = Ph ( 8 ); M = Ga R = CH 3, R‘ = CH 3 ( 10 )) are described. Compounds 1 − 6 were prepared by the reaction of MMe 3 (M = Al, Ga) with 2-acetylpyridine 4-alkylthiosemicarbazone in toluene. Compounds 7 − 10 were prepared using MMe 3 (M = Al, Ga) in toluene with acetophenone 4-alkylthiosemicarbazone under anaerobic conditions. These compounds, 1 − 10, have been characterized by microanalysis, NMR ( 1 H, 13 C, 27 Al) spectroscopy, and single-crystal X-ray diffraction. X-ray single-crystal diffraction analyses reveal that compound 3 is a dinuclear aluminum compound with coordination numbers of five and four and compound 8 is a dinuclear gallium compound in which each gallium atom is four-coordinate.