Photoinduced electron transfer in ion pairs

Billing, Roland; Rehorek, Detlef; Hennig, H.

doi:10.1007/3-540-52568-8_4

Cited by 80 publications

(39 citation statements)

References 187 publications

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“…these ancillary dithiolate ligands in many organometallic compounds has been reported to function as both models for magnetic and superconducting materials 4 and electron-transfer processes involving biological systems. 5 As an extension to our above dithiolate compounds, we next decided to prepare complexes bearing an oxygen ligand in place of each sulfur group. One such oxygen analog that has been successfully prepared in our laboratories has been isolated from the reaction between Cp*Ru(NO)CI2 and the heterocyclic diol compound 2,3-quinoxalinediol in methanol solution.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, extended Hückel molecular orbital calculations, and X-ray diffraction structure of the pentamethylcyclopentadienylruthenium complex Cp*Ru(NO)(2,3-quinoxalinediolate)

1995

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The reaction between Cp*Ru(NO)CI2 and the heterocyclic compound 2,3-quinoxalinediol in the presence of methanolic KOH leads to the formation of the new piano-stool compound Cp*Ru(NO)(2,3-quinoxalinediolate) (1). Product isolation and characterization by solution spectroscopic methods (IH and ~3C NMR and IR) are described. The solid-state structure of Cp*Ru(NO)(2,3-quinoxalinediolate) confirms the replacement of each chloride ligand in Cp*Ru(NO)CI2 by an oxygen group of the 2,3-quinoxalinediol ligand. Cp*Ru(NO)(2,3-quinoxalinediolate) crystallizes in the orthorhombic space group Pbca, a = 14.846 (1)

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Section: Introductionmentioning

confidence: 99%

Synthesis, extended Hückel molecular orbital calculations, and X-ray diffraction structure of the pentamethylcyclopentadienylruthenium complex Cp*Ru(NO)(2,3-quinoxalinediolate)

1995

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“…In the context of the present study it should be noted that photochemical reductive eliminations of [Pt IV (CN) 4 X 2 ] 2À with X À = halide and azide initiated by LMCT excitation are well known to yield [Pt II (CN) 4 ] 2À [8,9]. 4 ] 2À is photochemically and thermally very stable in solution [8,9] and displays a characteristic absorption spectrum with k max = 278 (e = 1600 M À1 cm À1 ), 254 (12 300), 239 (sh, 1800) and 215 (22 500) nm. Addition of diluted acids does not change this spectrum nor does it affect the thermal or photochemical stability of [Pt(CN) 4 ] 2À .…”

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confidence: 98%

“…Accordingly, N 2 H þ 5 and N 2 H 2þ 6 in combination with a reducing anion are expected to form redox-active ion pairs. Such ion pairs are characterized by outer-sphere charge transfer (OSCT) absorptions [2][3][4][5]. We explored this possibility and selected the ion pair N 2 H 2þ 6 This photoreaction would be rather interesting in its own right.…”

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confidence: 98%

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Photochemical oxidative addition of hydrazinium cations to tetracyanoplatinate(II) induced by OSCT excitation

Kunkely

Vogler

2008

Inorganic Chemistry Communications

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“…In many cases our own observations are discussed in order to provide a competent review. Outer sphere (or intermolecular) CT interactions [12][13][14][15][16][17][18] are omitted since they are treated elsewhere in this book.…”

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Charge Transfer Excitation of Coordination Compounds. Generation of Reactive Intermediates

Vogler

Kunkely

1993

Catalysis by Metal Complexes

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Reactive compounds exhibit frequently catalytic properties. Particularly, many reactive metal complexes are characterized by their catalytic activity. Photochemistry presents one of the most important and versatile methods for the generation of reactive compounds. The design of photochemically generated catalysts requires a deeper insight in the photochemistry in general. The choice of appropriate light-sensitive precursors can be guided by several considerations. A straight-forward approach involves the selection of compounds according to the type of electronic excitation which often predetermines the nature of the photoproducts.In a metal complex the metal-ligand bonds are generally polar. The molecular orbitals are then not equally delocalized between metal and ligands but predominantly located at the metal or the ligands. The electronic transitions are classified according to this localization [1]. In simple homoleptic mononuclear complexes three types of electronic excitations can be distinguished. Electronic transitions are localized at the metal (metalcentered, MC), at the ligand (ligand-centered, LC or intraligand, IL) or they take place between MOs at the metal and the ligand. The latter transitions are associated with a spatial redistribution of electrons and therefore are termed charge transfer (CT) transitions. While this review deals with CT excited states let us first have a short look at MC and LC states and their significance for the generation of reactive species which might be catalytically active.Since the valence orbitals of metals may be of the s, p, d, and f type all these orbitals can be involved in MC transitions. Ligand field (LF) or dd excited states have been investigated in great detail [2][3][4][5][6]. In many cases LF (or dd) excitation leads to a weakening of metal-ligand bonds. As a result a ligand may be released without any change of the oxidation state of the metal. This process is very important for the generation of catalysts because the product is a coordinatively unsaturated complex which provides an

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Photoinduced electron transfer in ion pairs

Cited by 80 publications

References 187 publications

Synthesis, extended Hückel molecular orbital calculations, and X-ray diffraction structure of the pentamethylcyclopentadienylruthenium complex Cp*Ru(NO)(2,3-quinoxalinediolate)

Synthesis, extended Hückel molecular orbital calculations, and X-ray diffraction structure of the pentamethylcyclopentadienylruthenium complex Cp*Ru(NO)(2,3-quinoxalinediolate)

Photochemical oxidative addition of hydrazinium cations to tetracyanoplatinate(II) induced by OSCT excitation

Charge Transfer Excitation of Coordination Compounds. Generation of Reactive Intermediates

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