Photochemical Redox Reaction of Aqueous Benzylpentacyanocobaltate(III)

Vogler, Arnd; Hirschmann, R.

doi:10.1515/znb-1976-0817

Cited by 9 publications

(3 citation statements)

References 7 publications

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“…Accordingly, the photoredox decomposition of Co(III) pentaammine complexes proceeds by equation (4) In the case of Co in (CN) 5 X 3 -such a photoredox decomposition is not expected to take place since the primary complex fragment Co II (CN)5 3_ does not decay but undergoes a recombination with X-(or X 2 ) [94], However, if the ligand radical reacts rapidly and irreversibly Co(CN)5X 3 " will also yield stable photoredox products, e.g. (X = benzyl) [96]:…”

Section: Cobalt(iii) Complexesmentioning

confidence: 99%

“…Such processes lead to a further variation of the photoproducts. Insertion or addition [96,100] [Co m (CN) 5 …”

Section: Cobalt(iii) Complexesmentioning

confidence: 99%

“…For example, methyl and benzyl radicals are generated by the photolysis of Re0 3 (Me) [22] and Co(CN)5(benzyl) 3_ [96] respectively. Many other ligand radicals are produced by homolysis (see also above).…”

Section: Ligand-based Radicalsmentioning

confidence: 99%

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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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Section: Cobalt(iii) Complexesmentioning

confidence: 99%

“…Such processes lead to a further variation of the photoproducts. Insertion or addition [96,100] [Co m (CN) 5 …”

Section: Cobalt(iii) Complexesmentioning

confidence: 99%

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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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Of Cobalt

Ford¹

1986

Inorganic Reactions and Methods

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Mechanistic Aspects of the Photosubstitution and Photoisomerization Reactions of d ⁶ Metal Complexes

Ford¹,

Wink²,

DiBenedetto³

1983

Progress in Inorganic Chemistry

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Photochemical Redox Reaction of Aqueous Benzylpentacyanocobaltate(III)

Cited by 9 publications

References 7 publications

Charge Transfer Excitation of Coordination Compounds. Generation of Reactive Intermediates

Charge Transfer Excitation of Coordination Compounds. Generation of Reactive Intermediates

Of Cobalt

Mechanistic Aspects of the Photosubstitution and Photoisomerization Reactions of d ⁶ Metal Complexes

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Photochemical Redox Reaction of Aqueous Benzylpentacyanocobaltate(III)

Cited by 9 publications

References 7 publications

Charge Transfer Excitation of Coordination Compounds. Generation of Reactive Intermediates

Charge Transfer Excitation of Coordination Compounds. Generation of Reactive Intermediates

Of Cobalt

Mechanistic Aspects of the Photosubstitution and Photoisomerization Reactions of d 6 Metal Complexes

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Mechanistic Aspects of the Photosubstitution and Photoisomerization Reactions of d ⁶ Metal Complexes