Half-sandwich manganese complexes Cp(CO)2Mn(NHC) as redox-active organometallic fragments

Abstract

Oxidation of the half-sandwich Mn^I complexes Cp(CO)₂Mn(NHC) bearing dialkyl-, arylalkyl- and diarylsubstituted N-heterocyclic carbene ligands (NHC = IMe, IMeMes, IMes) affords the corresponding stable Mn^II radical cations [Cp(CO)₂Mn(NHC)](BF₄) isolated in 92–95% yield. Systematic X-ray diffraction studies of the series of Mn^I and Mn^II NHC complexes revealed the expected characteristic structural changes upon oxidation, namely the elongation of the Mn–CO and Mn–NHC bonds as well as the diminution of the OC–Mn–CO angle. ESR spectra of [Cp(CO)₂Mn(IMes)](BF₄) in frozen solution (CH₂Cl₂/toluene 1 : 1, 70 K) allowed the identification of two conformers for this complex and their structural assignment using DFT calculations. The stability of these NHC complexes in both metal oxidation states, moderate oxidation potentials and the ease of detection of Mn^II species by a variety of spectroscopic techniques (UV-Vis, IR, paramagnetic ¹H NMR, and ESR) make these compounds promising objects for applications as redox-active organometallic fragments.