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Chemistry of Ruthenium. Part 4. trans-Dihalogeno(isonitrosoketone)(isonitrosoketonato)ruthenium(III). Structure and Stability, Electron Spin Resonance, Electron Transfer, and Proton Transfer

DOI: 10.1039/DT9820000615

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 615 - 622 (1982)

Update date:2022-08-05

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Authors:

Chakravarty, Akhil RanjanChakravarty, Akhil Ranjan

Chakravorty, AnimeshChakravorty, Animesh

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Article abstract of DOI:10.1039/DT9820000615

A group pf ruthenium(III) complexes of type is reported .The RuX2 group is trans and the hydrogen-bonded (HL)(L) moiety acts as a planar tetradentate chelator.The low CO stretching frequencies and better stability of R' = Ph versus R' = Me species are rationalised in terms of ionic resonance.The complexes display ligand to metal charge-transfer (l.m.c.t.) transitions at relatively low energies (500-800 nm).They are uniformly low-spin (S = 1/2) and have axial e.s.r. spectra.The g parameters (g(*) ca. 1.86, g(*) ca.2.50) are used to compute tetragonality (Δ), orbital reduction (k), and other parameters within the basic framework of crystal-field theory.The d-orbital order dxz, dyz < dxy < dz2 < dz2-y2 with the hole in dxy is indicated.The possible role of l.m.c.t. contribution in making both k and g(*) large is discussed. undergoes a reversible one-electron electrochemical reduction to blue (1-).This species can also be generated chemically.The redox process has been thoroughly studied using cyclic voltammetry and phase-sensitive alternating current voltammetry.Formal potential (ca. 0.4 V), diffusion coefficient, and heterogeneous rate-constant data are presented.Addition of NEt3 deprotonates to (1-).Reprotonation occurs on adding HClO4.Deprotonation dramatically affects the electrochemical response.In this context the symbiotic relationship between electron transfer and proton transfer is noted.

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