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Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes.

ABSTRACT: Previously, we reported the synthesis of Ti[N( o-(NCH₂P( ⁱPr)₂)C₆H₄)₃] and the Fe-Ti complex, FeTi[N( o-(NCH₂P( ⁱPr)₂)C₆H₄)₃], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc⁺), respectively. Two isostructural redox members, [FeTiL]⁺ and [FeTiL]^- (2^ox and 2^red, respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL]⁺ complex (1^ox). The solid-state structures of the [FeTiL]^+/0/- series feature short metal-metal bonds, ranging from 1.94-2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and ⁵⁷Fe Mössbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL]^+,0,- series are primarily Fe-based and that the polarized Fe-Ti ?-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).

SUBMITTER: Moore JT

PROVIDER: S-EPMC6727590 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Chemical flexibility of heterobimetallic Mn/Fe cofactors: R2lox and R2c proteins.

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| S-EPMC6643937 | biostudies-literature

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| S-EPMC8418555 | biostudies-literature

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