Organometallic photochemistry

Geoffroy, Gregory L.

doi:10.1021/ed060p861

Cited by 80 publications

(127 citation statements)

References 11 publications

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“…Unfortunately, the majority of metal complexes is not emissive. Those complexes which are luminescent [2][3][4][5][6]74,75] are mostly diamagnetic in the ground state. Generally, the emission originates from the energetically lowest triplet state.…”

Section: Emission From Charge Transfer Statesmentioning

confidence: 99%

“…In rare cases a fluorescence originating from the lowest-energy singlet is also observed. Irrespective of the spin multiplicity the luminescence of metal complexes may occur from all types of excited states including IL and MC states [2][3][4][5][6]74,75]. The emitting CT states are classified according to the labels which refer to the transitions in absorption.…”

Section: Emission From Charge Transfer Statesmentioning

confidence: 99%

“…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.…”

mentioning

confidence: 99%

“…Binuclear complexes with a covalent metal-metal bond can be split homolytically by a b M . M -> a*M-M excitation [4,7]. For example, the photolysis of Mn 2 (CO)io yields Mn(CO)5 radicals which recombine or engage in secondary reactions [4,7].…”

mentioning

confidence: 99%

“…M -> a*M-M excitation [4,7]. For example, the photolysis of Mn 2 (CO)io yields Mn(CO)5 radicals which recombine or engage in secondary reactions [4,7]. Much less is known on the photochemistry of MC excited states of the sp [8], pp [8], ds [9], dp or ff [2,10] type.…”

mentioning

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: Emission From Charge Transfer Statesmentioning

confidence: 99%

Section: Emission From Charge Transfer Statesmentioning

confidence: 99%

“…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.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

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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Nucleophilic addition versus electron transfer in carbonylmetallate salts. Donor-acceptor interactions in the precursor ion pairs

Bockman¹,

Kochi²

1997

J. Phys. Org. Chem.

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The isostructural pentacarbonylmetallate anions M(CO)ϪϪ 5 ] is identified as the critical precursor for both electron transfer and nucleophilic coupling. Based on these observations, it is proposed that the rates and mechanisms of these interionic reactions are controlled by donor-acceptor bonding in the transition states, which in turn is directly related to the charge-transfer interactions extant in the ion-pair intermediate. ©

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The Photochemistry of (Diene)(hydro)[tris(3,5-dimethylpyrazolyl)borato]rhodium Complexes, Preliminary Communication

Ferrari

Merlin

Sostero

et al. 1999

HCA

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The photochemical rearrangement of [Rh(η4‐1,5‐cod)TpMe2](TpMe2=hydrotris(3,5‐dimethylpyrazolyl)borato, 1,5‐cod=cycloocta‐1,5‐diene) to the new compound [Rh(η4‐1,3‐cod)TpMe2] (2) is described. The characterization of 2 was carried out using 1H‐, 13C‐, and 103Rh‐HMQC‐NMR spectroscopy. Photolysis of 2 is a versatile entry point into the organometallic chemistry of the {RhTpMe2} fragment as it can be used to produce a) hydrido‐carbonyl ([Rh(CO)H2TpMe2]), b) hydrido‐phenyl‐phosphite ([RhH(Ph)(P(OMe)3)TpMe2]), and c) ethoxide‐hydrido‐phosphite ([RhH(OEt)(P(OMe)3)TpMe2]) complexes.

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Organometallic photochemistry

Abstract: A discussion of photosubstitution chemistry in organometallic molecules. From the State-of-the-Art Symposium: Inorganic Photochemistry, held at the ACS meeting, Seattle, 1983.

Cited by 80 publications

References 11 publications

Charge Transfer Excitation of Coordination Compounds. Generation of Reactive Intermediates

Charge Transfer Excitation of Coordination Compounds. Generation of Reactive Intermediates

Nucleophilic addition versus electron transfer in carbonylmetallate salts. Donor-acceptor interactions in the precursor ion pairs

The Photochemistry of (Diene)(hydro)[tris(3,5-dimethylpyrazolyl)borato]rhodium Complexes, Preliminary Communication

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