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Keywords:

  • Manganese;
  • Catalysts­;
  • Chelates;
  • Redox chemistry;
  • Non-innocent ligands­

Abstract

The synthesis and electronic structure of reduced aryl-substituted bis(imino)pyridine manganese compounds have been explored. Stirring a THF slurry of [(iPrPDI)MnCl2] {iPrPDI = 2,6-(2,6-iPr2–C6H3N=CMe)2C5H3N} with excess Na and catalytic (0.5 mol-%) naphthalene furnished the bis(THF) compound [(iPrPDI)Mn(THF)2]. Performing the reduction with excess Na(Hg) in toluene furnished the bis(chelate) manganese compound [(iPrPDI)2Mn]. For both compounds, a combination of EPR spectroscopy, magnetic measurements and metrical parameters determined from X-ray diffraction established high-spin MnII compounds with reduced, redox-active bis(imino)pyridine ligands. Substitution of the THF ligands with carbon monoxide yielded [(iPrPDI)Mn(CO)2], a low-spin MnI, d6 compound with an experimentally observed bis(imino)pyridine-centred radical. Oxidation and reduction of this compound furnished [(iPrPDI)Mn(CO)3]+ and [(iPrPDI)Mn(CO)2], respectively, and provided a series of three manganese carbonyl compounds over three oxidation states. Elucidation of the electronic structure of these compounds established that oxidation events within the series are ligand- rather than manganese-based, most likely a result of the stable low-spin MnI, d6 electron configuration imparted by the strong-field carbonyl ligands.