The underappreciated influence of ancillary halide on metal-ligand proton tautomerism.

ABSTRACT: Syntheses of Vaska-type complexes [IrP₂X(CO)] (P = phosphine, X = halide) with all four common halides (fluoride, chloride, bromide, and iodide) was attempted using a protic and hemilabile imidazolyl di-tert-butyl phosphine ligand. In the solid-state, all four complexes were found to be ionic with the halides in the outer-sphere, and the fourth coordination site of the square plane occupied by the imidazole arm of the ligand. In solution, however, the chloride complex was found to be in equilibrium with an octahedral Ir^III-H species at room temperature. For the bromide and iodide analogs, the corresponding Ir^III-H species were also observed but only after heating the solutions. The neutral Ir^I Vaska's analogs for X = Cl, Br, and I were obt

SUBMITTER: Jain AK 

PROVIDER: S-EPMC9258501 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature