The Electron-Rich {Ru(acac)2} Directed Varying Configuration of the Deprotonated Indigo and Evidence for Its Bidirectional Noninnocence

Inorganic Chemistry
Prasenjit MondalGoutam Kumar Lahiri

Abstract

This article highlights the hitherto unexplored varying binding modes of the deprotonated natural dye indigo (H2L) and its bidirectional noninnocent potential. The reaction of H2L with the selective metal precursor Ru(II)(acac)2(CH3CN)2 (acac(-) = acetylacetonate) leads to the simultaneous formation of paramagnetic Ru(III)(acac)2(HL(-)) (1; blue solid) and diamagnetic Ru(II)(acac)2(L) (2; red solid), which have been characterized by standard analytical, spectroscopic, and structural analysis. Crystal structures establish that the usual trans configurated and twisted monodeprotonated HL(-) and unprecedented cis configurated nearly planar dehydroindigo (L) bind to the {Ru(acac)2} metal fragment via the N(-),O and N,N donors, forming six- and five-membered chelates, respectively. It also reveals the existence of intramolecular N-H···O hydrogen-bonding interaction between the NH proton and C═O group at the back face of the coordinated HL(-), in addition to an intermolecular N-H···O hydrogen bonding between the NH proton of HL(-) of Molecule B and oxygen atom of the nearby acac of the second molecule (Molecule A) in the asymmetric unit of 1. The specific role of the electron-rich {Ru(acac)2} metal fragment in stabilizing the cis-con...Continue Reading

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