Variable Coordination Modes of Potentially Tetradentate Phosphino‐ and Arsinoarylthiolato Ligands Derived from E (2‐SHC 6 H 4 ) 3 ( E = P, As) in Gallium(III) Complexes

P(2‐SHC 6 H 4 ) 3 ( PS 3 H 3 ) reacts with GaMe 3 (1:1) to give GaMe{P(2‐SC 6 H 4 ) 2 (2‐SHC 6 H 4 )‐κ 3 S , S′,P } ( 1 ), which could be deprotonated with NEt 3 to give [NEt 3 H][GaMe{P(2‐SC 6 H 4 ) 3 ‐κ 3 S , S′,P }] ( 2 ). The 1:2 reaction of E (2‐SHC 6 H 4 ) 3 [ E = P ( PS 3 H 3 ), As ( AsS 3 H 3 )] with GaMe 3 gave the dinuclear complexes GaMe{ E (2‐SC 6 H 4 ) 2 (2‐S{GaMe 2 (THF)}C 6 H 4 )‐κ 3 S , S′,E } [ E = P ( 3 ), As ( 4 )]. Serendipitous hydrolysis of 4 resulted in small amounts of the hexanuclear gallium hydroxide complex cyclo ‐{GaMe(μ‐OH)} 6 {As(2‐SC 6 H 4 ) 3 ‐κ S , S′,S′′ } 2 ( 5 ). Complexes 1 – 4 were fully characterized, complexes 2 – 5 also by X‐ray crystallography.