Synthesis, structure, and electronic properties of RuN 6 dinuclear Ru-Hbpp complexes

Stephan Roeser, Mehmed Z. Ertem, Clyde Cady, Rainer Lomoth, Jordi Benet-Buchholz, Leif Hammarström, Biprajit Sarkar, Wolfgang Kaim, Christopher J. Cramer, Antoni Llobet

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Abstract

A series of RuN 6 dinuclear Ru-Hbpp complexes (Hbpp is the dinucleating tetraaza ligand 3,5-bis(pyridyl)pyrazole) of general formula {[Ru II(R 2-trpy)(MeCN)] 2(μ-R 1-bpp)} 3+, 10 3+-14 3+, (R 1 = H, Me, or NO 2. and R 2 = H, Me, MeO; see Scheme 1) has been prepared from their Cl - or AcO - bridged precursors. The complexes have been characterized by UV-vis, NMR, CV, and some by X-ray. Complexes 10 3+-14 3+, Ru 2 II,II, were oxidized by 1 equiv in solution, leading to the mixed valence Ru 2 II,III complexes 10 4+-14 4+ containing one unpaired electron and were characterized by EPR and UV-vis-near-IR, which showed metal-centered spin and the presence of low-energy IVCT bands. The H ab parameter indicates a relatively strong electronic coupling between the two ruthenium centers (class II). Further two electron oxidation in solution of the 10 3+-14 3+ led to the formation of EPR silent Ru 2 III,III complexes 10 5+-14 5+, that were further characterized by UV-vis-NIR. TD-DFT calculations are employed to assign the nature of the UV-vis transitions for the complexes in the various oxidation states, which are of metal to ligand charge transfer (MLCT) type for Ru 2 II,II and ligand to metal charge transfer (LMCT) type for Ru 2 III,II and Ru 2 III,III.

Original languageEnglish
Pages (from-to)320-327
Number of pages8
JournalInorganic Chemistry
Volume51
Issue number1
DOIs
Publication statusPublished - Jan 2 2012

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Electronic properties
Metals
Ligands
ligands
Paramagnetic resonance
Charge transfer
synthesis
charge transfer
electronics
metals
Oxidation
oxidation
Ruthenium
Electrons
Discrete Fourier transforms
Band structure
ruthenium
energy bands
electrons
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Roeser, S., Ertem, M. Z., Cady, C., Lomoth, R., Benet-Buchholz, J., Hammarström, L., ... Llobet, A. (2012). Synthesis, structure, and electronic properties of RuN 6 dinuclear Ru-Hbpp complexes. Inorganic Chemistry, 51(1), 320-327. https://doi.org/10.1021/ic201668r

Synthesis, structure, and electronic properties of RuN 6 dinuclear Ru-Hbpp complexes. / Roeser, Stephan; Ertem, Mehmed Z.; Cady, Clyde; Lomoth, Rainer; Benet-Buchholz, Jordi; Hammarström, Leif; Sarkar, Biprajit; Kaim, Wolfgang; Cramer, Christopher J.; Llobet, Antoni.

In: Inorganic Chemistry, Vol. 51, No. 1, 02.01.2012, p. 320-327.

Research output: Contribution to journalArticle

Roeser, S, Ertem, MZ, Cady, C, Lomoth, R, Benet-Buchholz, J, Hammarström, L, Sarkar, B, Kaim, W, Cramer, CJ & Llobet, A 2012, 'Synthesis, structure, and electronic properties of RuN 6 dinuclear Ru-Hbpp complexes', Inorganic Chemistry, vol. 51, no. 1, pp. 320-327. https://doi.org/10.1021/ic201668r
Roeser, Stephan ; Ertem, Mehmed Z. ; Cady, Clyde ; Lomoth, Rainer ; Benet-Buchholz, Jordi ; Hammarström, Leif ; Sarkar, Biprajit ; Kaim, Wolfgang ; Cramer, Christopher J. ; Llobet, Antoni. / Synthesis, structure, and electronic properties of RuN 6 dinuclear Ru-Hbpp complexes. In: Inorganic Chemistry. 2012 ; Vol. 51, No. 1. pp. 320-327.
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AU - Benet-Buchholz, Jordi

AU - Hammarström, Leif

AU - Sarkar, Biprajit

AU - Kaim, Wolfgang

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N2 - A series of RuN 6 dinuclear Ru-Hbpp complexes (Hbpp is the dinucleating tetraaza ligand 3,5-bis(pyridyl)pyrazole) of general formula {[Ru II(R 2-trpy)(MeCN)] 2(μ-R 1-bpp)} 3+, 10 3+-14 3+, (R 1 = H, Me, or NO 2. and R 2 = H, Me, MeO; see Scheme 1) has been prepared from their Cl - or AcO - bridged precursors. The complexes have been characterized by UV-vis, NMR, CV, and some by X-ray. Complexes 10 3+-14 3+, Ru 2 II,II, were oxidized by 1 equiv in solution, leading to the mixed valence Ru 2 II,III complexes 10 4+-14 4+ containing one unpaired electron and were characterized by EPR and UV-vis-near-IR, which showed metal-centered spin and the presence of low-energy IVCT bands. The H ab parameter indicates a relatively strong electronic coupling between the two ruthenium centers (class II). Further two electron oxidation in solution of the 10 3+-14 3+ led to the formation of EPR silent Ru 2 III,III complexes 10 5+-14 5+, that were further characterized by UV-vis-NIR. TD-DFT calculations are employed to assign the nature of the UV-vis transitions for the complexes in the various oxidation states, which are of metal to ligand charge transfer (MLCT) type for Ru 2 II,II and ligand to metal charge transfer (LMCT) type for Ru 2 III,II and Ru 2 III,III.

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