P-Block metal complexes with bis(pyrazol-1-yl)acetato ligands.

Abstract

The hetereoscorpionate ligands bis(pyrazol-1-yl)acetic acid (Hbpza) and bis(3,5-dimethylpyrazol-1-yl)acetic acid (Hbdmpza) are reacted with [Sn(OAc)2] or [Sn(acac)2] to yield the corresponding Sn(II) complexes. A single crystal X-ray determination for the in solution monomeric complex [Sn(bpza)2] (1a) revealed a dinuclear molecular structure [Sn2(bpza)4] (1b), with κ3-N,N,O-coordinated bpza ligands at each of the Sn(II) and two bpza ligands μ-bridging between the Sn(II) centres. The molecular structure of [Sn(bdmpza)2] (2) exhibits a homoleptic bisligand complex with both ligands displaced by the free electron pair, which is proven by DFT calculations. Oxidation of complex 2 in an attempt to synthesize a homoleptic Sn(IV) complex leads to the formation of [Sn(bdmpza)F3] (3). In addition, homoleptic bisligand gallium complexes [Ga(bdmpza)2][ClO4] (4) and [Ga(bpza)2][GaCl4] (5) were prepared and characterized by 71Ga NMR and IR spectroscopy as well as by X-ray crystallography.