Half-sandwich manganese complexes Cp(CO)2Mn(NHC) as redox-active organometallic fragments. Issue 40 (23rd September 2021)

• Record Type: Journal Article
• Authors: Brousses, Rémy; Maurel, Vincent; Mouesca, Jean-Marie; César, Vincent; Lugan, Noël; Valyaev, Dmitry A.
• Is Part Of: Dalton transactions. Volume 50:Issue 40(2021)
• Page Start: 14264
• Page End: 14272
• Publication Date: 2021-09-23
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt02182f
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : One-electron oxidation of Mn I NHC complexes affords stable 17-electron Mn II radical cations. The influence of NHC substituents on spectroscopic properties and conformational behavior within the series of Mn I /Mn II species was systematically studied. Abstract : Oxidation of the half-sandwich Mn I complexes Cp(CO)2 Mn(NHC) bearing dialkyl-, arylalkyl- and diarylsubstituted N-heterocyclic carbene ligands (NHC = IMe, IMeMes, IMes) affords the corresponding stable Mn II radical cations [Cp(CO)2 Mn(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)2 Mn(IMes)](BF4 ) in frozen solution (CH2 Cl2 /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 1 H NMR, and ESR) make these compounds promising objects for applications as redox-active organometallic fragments.