The multi-electron conversion of small molecules is readily accomplished in Nature at high spin polynuclear metal assemblies nestled in metalloenzyme cores (ex. nitrogenase, oxygen evolving complex). The close proximity of several metal centers in these complexes provides multiple metal-substrate binding sites, while facilitating multi-electron redox processes associated with small molecule conversion.Our approach has focused on using flexible multinucleating ligands composed of weak-field hexa-amine binding sites (1,3,5-C6H9(NHPh-o-NHSiMe2tBu)3: tbsLH6 ) to direct the formation of predesigned multinuclear architectures, such as the reported tbsLM3(thf)  (M  = Fe, Mn) or mixed-metal tbsLFe2Mn(thf)  complexes.1 This talk will describe recent progress in the synthesis of complexes with two transition metals and a redox inactive Lewis acid (LA) incorporated in the same proximal space. Incorporation of a LA (Ca or Sr) has resulted in the stabilization of a tbsLFe2LA(�-O)  species, previously inaccessible using the tbsLFe3(thf)  platform. Further efforts to synthesize LA-stabilized reactive linkages, such as Cu�O�Cu or Fe�C�Fe, through oxidative multi-electron group transfer chemistry will be described, as well as their subsequent reactivity with small molecules. (1)        Powers, T. M.; Gu, N. X.; Fout, A. R.; Baldwin, A. M.; Hern�ndez S�nchez, R.; Alfonso, D. M.; Chen, Y.-S.; Zheng, S.-L.; Betley, T. A. J. Am. Chem. Soc. 2013 , 135, 14448-14458.

Polynuclear metal complexes for multi-electron reactions

247th National Meeting (2014)

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