Abstract

Monoanionic mixed N2P2 donor beta-diketiminate (BDI) ligands with phosphine pendant arms, 2-(4-tolyl)-bis(2-diisopropylphosphinophenyl)propenediimine (abbreviated as Tol-BDI(DIPPP)2H), were prepared and metallated with zinc(II) iodide. Three ligand variations have been synthesized by incorporating different substituents (methyl or methoxy) on the linker phenyl rings at positions 4 and 6. In the 4-methyl zinc complex [Tol-BDI(DIPPMeP)2ZnI] and 4-methoxy zinc complex [Tol-BDI(DIPPMeOP)2ZnI], the metal is bound to all four donors on the ligand, rendering a distorted square pyramidal geometry around the zinc metal with τ5 values of 0.25 and 0.29, respectively. However, the crystal structure of the 4,6-dimethyl zinc complex [Tol-BDI(DIPPMe2P)2ZnI] shows a four-coordinate zinc with only one phosphine bound to the metal, resulting in a distorted seesaw geometry around the metal. While X-ray crystallography shows no interactions between the metal center and the unbound phosphine, solution characterization reveals a symmetrical complex with both phosphines bound to the metal center in all three zinc complexes.

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