The (β‐Diketiminato)bismuth(III) Complex [LBiCl(μ‐Cl)] 2 {L = HC[(CMe)(NAr)] 2 , Ar = 2,6‐ i Pr 2 C 6 H 3 } and Its Derivatives: The Presence of Versatile Ligand Ligation Modes

The reaction of BiCl 3 with LLi {L = HC[(CMe)(NAr)] 2 , Ar = 2,6‐ i Pr 2 C 6 H 3 } in a molar ratio of 1:1 was carried out under various conditions and afforded [LBiCl(μ‐Cl)] 2 ( 1 ), [L′BiCl(μ‐Cl)] 2 [ 4 ; L′ = N(Ar)=C(Me)CH=C(NHAr)CH 2 ], and L″Bi 2 Cl 4 [ 5 ; L″ = N(Ar)=C(Me)CC(Me)=N(Ar)]. Compounds 1 and 4 are isomers, and a thermal conversion of 1 to 4 was realized. In this reaction system, when a little excess n BuLi and BiCl 3 were used, [LBiCl(μ‐Cl)Bi( n Bu)Cl(μ‐Cl)] 2 ( 2 ) was isolated as side product after the isolation of 1 . The reaction of 1 with AgOOCCF 3 in the absence of light from –15 °C to room temperature generated LBi(OOCCF 3 ) 2 ( 3 ). Finally, the solvent‐free reaction of BiCl 3 and LH at elevated temperature (125 °C) under vacuum gave [LH 2 ] + [BiCl 4 (THF)] – ( 6 ) in a low yield. The formulations of all these complexes have been confirmed by 1 H and 13 C NMR spectroscopy and X‐ray crystallography, except for 6 , which was only identified by X‐ray crystallography due to its insolubility in organic solvents. These complexes exhibit versatile L ligation modes at the metal atom and reveal the complexity of the reaction between BiCl 3 and LLi.