Inter-ligand intramolecular through-space anisotropic shielding in a series of manganese carbonyl phosphorous compounds

Abstract

Eight novel manganese carbonyl complexes of the type [Mn(bpy-^tBu)(CO)₃PR₃]⁺ (bpy-^tBu = 4,4′-di-tert-butyl-2,2′-bipyridine; R = Cy, ⁿBu, Me, p-tol, Ph, p-F-Ph, OEt, and OMe), have been synthesized and characterized by ¹H NMR, FTIR, UV/Vis, HRMS and CV. X-ray crystallographic structures of [Mn(bpy-^tBu)(CO)₃(PCy₃)]⁺ and [Mn(bpy-^tBu)(CO)₃(PPh₃)]⁺ were obtained. The short Mn–P bond length allows for close proximity of the bipyridine ligand and the phosphine R groups, resulting in strong anisotropic shielding of certain bipyridine protons by aryl R groups (reordering the bipyridine ¹H NMR pattern in the most extreme case). Electrochemical analysis of the compound series reveals that while each is a competent precatalyst for electrochemical carbon dioxide reduction (to carbon monoxide), the lability of the PR₃ ligand results in similar catalytic performance amongst the series.