Chemical switching behaviour of tricarbonylrhenium(i) complexes of a new redox active ‘Pincer’ ligand

Wanniarachchi, Sarath; Liddle, Brendan J.; Toussaint, J.; Lindeman, Sergey V.; Bennett, Brian; Gardinier, James R.

doi:10.1039/c001344g

Cited by 34 publications

(38 citation statements)

References 17 publications

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“…The shape and energies of these pi-radical bands are nearly identical to those found in the rhenium(I) or rhodium(III) complexes of this oxidized ligand. 24,25 …”

Section: Resultsmentioning

confidence: 99%

“…The coordination chemistry of tricarbonylrhenium(I) 24 and rhodium 25 complexes showed that these pincer-type ligands are electrochemically active and chemically non-innocent. The electronic properties and reactivity of the complexes could be predictably fine-tuned by substituting at the pyrazolyl, at the para -aryl positions, or even at the metal center.…”

Section: Introductionmentioning

confidence: 99%

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Electronic Communication Across Diamagnetic Metal Bridges: A Homoleptic Gallium(III) Complex of a Redox-Active Diarylamido-Based Ligand and Its Oxidized Derivatives

et al. 2012

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Complexes with cations of the type [Ga(L)2]n+ where L = bis(4-methyl-2-(1H-pyrazol-1-yl)phenyl)amido and n = 1, 2, 3 have been prepared and structurally characterized. The electronic properties of each were probed by electrochemical and spectroscopic means and were interpreted with the aid of DFT calculations. The dication, best described as [Ga(L−)(L0)]2+, and is a Robin-Day class II mixed-valence species. As such, a broad, weak, solvent-dependent intervalence charge transfer (IVCT) band was found in the NIR spectrum in the range 6390 to 6925 cm−1, depending on solvent. Band shape analyses and the use of Hush and Marcus relations revealed a modest electronic coupling, Hab of about 200 cm−1, and a large rate constant for electron transfer, ket, on the order of 1010 s−1 between redox active ligands. The di-oxidized complex [Ga(L0)2]3+ shows a half-field ΔMs = 2 transition in its solid-state X-Band EPR spectrum at 5 K which indicates that the triplet state is thermally populated. DFT calculations (M06/Def2-SV(P)) suggest that the singlet state is 21.7 cm−1 lower in energy than the triplet state.

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“…The shape and energies of these pi-radical bands are nearly identical to those found in the rhenium(I) or rhodium(III) complexes of this oxidized ligand. 24,25 …”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Electronic Communication Across Diamagnetic Metal Bridges: A Homoleptic Gallium(III) Complex of a Redox-Active Diarylamido-Based Ligand and Its Oxidized Derivatives

et al. 2012

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“…Since multiple states characterize redox-active groups, future applications in magnetism (bistable switching) can be envisioned, [68] as can applications as ATRP catalysts, where redox potentials are of central importance.…”

Section: Discussionmentioning

confidence: 99%

Systematics and Future Projections Concerning Redox‐Noninnocent Amide/Imine Ligands

Caulton

2011

Eur J Inorg Chem

121

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An analysis of the conjugative possibilities of dienes carrying two terminal heteroatom donors shows some generalizations of these as possible redox‐active (redox “noninnocent”) ligands. If the two E=C functionalities (E = O,S, NR, CHR) are connected by an odd number of sp2‐hybridized atoms, full conjugation between the two terminal E donors is not possible, a situation which is found both in 2,6‐bis(imino)pyridine (BIMPY) and beta‐diketiminate ligands; the character of their redox noninnocence is thus altered, compared to 1,4‐diheterodienes. Some insight into the BIMPY ligand comes from the analog where one imino arm is absent. The traditional stereochemical relationships which govern conjugation in arenes are analyzed for their implications for different bis(imino)pyridine isomers, and also for 2,6‐dipyrimidyl‐ and dipyridazinyl‐pyridines, as generalizations of the classic terpyridyl ligands. Factors which favor oxidized vs. reduced ligand forms are discussed.

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“…[185][186][187][188] It was also observed that the chloride of one complex bonds to the adjacent complex through the acidic methylene CH (Cl/H ¼ 2.638(2)Å, Cl/C ¼ 3.569(7)Å), leading to the formation of a single-stranded linear polymer. A face-to-face p-stacking interaction (centroid-centroid distance of 3.736Å) occurs between the phenyl group and 1,2,3-triazole units on adjacent complexes to produce the double-stranded structure.…”

Section: 95mentioning

confidence: 99%

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

2018

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In recent years, metal complexes of organo 1,2,3-triazole click-derived ligands have attracted significant attention as catalysts in many chemical transformations and also as biological and pharmaceutical active agents. Regarding the important applications of these metal-organo 1,2,3-triazole-based complexes, in this review, we focused on the recently reported investigations of the structural, electronic, and spectroscopic aspects of the complexation process in transition metal complexes of 1,2,3-triazole-based click ligands. In line with this, the coordination properties of these triazole-based click ligands with transition metals were studied via several quantum chemistry calculations. Moreover, considering the complexation process, we have presented comparative discussions between the computational results and the available experimental data.

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Chemical switching behaviour of tricarbonylrhenium(i) complexes of a new redox active ‘Pincer’ ligand

Cited by 34 publications

References 17 publications

Electronic Communication Across Diamagnetic Metal Bridges: A Homoleptic Gallium(III) Complex of a Redox-Active Diarylamido-Based Ligand and Its Oxidized Derivatives

Electronic Communication Across Diamagnetic Metal Bridges: A Homoleptic Gallium(III) Complex of a Redox-Active Diarylamido-Based Ligand and Its Oxidized Derivatives

Systematics and Future Projections Concerning Redox‐Noninnocent Amide/Imine Ligands

Computational investigations of click-derived 1,2,3-triazoles as keystone ligands for complexation with transition metals: a review

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