The metal complexes of redox non-innocent ligand assembly has drawn continuing attention with reference to their unique electronic structural aspects and efficacy in metal mediated organic transformations.1 In this regard, BIAN (bis(arylimino)acenaphthene) derived metal complexes have found widespread application in important catalytic transformations2 due to its structural rigidity as well as efficient electron uptake at the vacant antibonding orbitals of naphthalene moiety thus enabling extended delocalization across the imine bond(C=N) and naphthalene framework.3 The present deliberation deals with the structurally characterized selective ruthenium complexes of BIAN and the corresponding in-situ generated partially hydrolyzed [N-(phenyl)imino]acenapthenone (BIAO) in combination with tridentate 2,2/:6/,2//-terpyridine/Cl/H2O co-ligands. Detailed experimental and theoretical calculation establishes following aspects: (i) tunability of 'R' group pushes the electron into the antibonding orbitals of of naphthalene i.e. beyond its α-diimine fragment resulting in a tetraanionic BIAN, (ii) The aqua derivatives act as an efficient pre-catalyst in oxidative transformation of olefins and alcohols to their respective epoxides and aldehydes via the involvement of {RuIV=O} as an active intermediate in both the processes.3

Electronic structure and multi-catalytic features of redox-active Bian (bis-(arylimino)acenaphthene) derived ruthenium complexes

254th National Meeting (2017)

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