Formazanido complexes of heavier group 13 elements aluminium, gallium, and indium

The preparation, molecular structures and physical properties of novel heavy group 13 metal formazanido complexes are described. The trimethyl derivatives MMe3 (M = Al, Ga, In) react with 1,3,5-triphenylformazan (Htpf) in a 1 : 1 ratio to give methane and metallacycles of the type [M(tpf)Me2]. While [Al(tpf)Me2] and [Ga(tpf)Me2] are mononuclear compounds with six-membered rings and coordination number 4 in solution and in the crystalline state, indium derivative [In(tpf)Me2] forms oligomers in non-coordinating solvents according to NMR studies, these are probably N-bridged dimers with coordination number 5 at indium. The oligomer is cleaved by addition of one equivalent of pyridine or 4-dimethylaminopyridine (DMAP). The complexes [M(tpf)Me2] (M = Al, Ga) and [In(tpf)Me2(DMAP)] are characterized by XRD analyses. They are unique examples of main group metal formazane ring systems of the third and higher periods. The UV-Vis solution spectra of the neutral ligand Htpf and its metallated compounds [M(tpf)Me2] (M = Al, Ga, In) are discussed.