Photochemistry of [MCo2(CO)8] (M = Zn, Cd, Hg) induced by metal to metal charge tranfer excitation

Vogler, Arnd; Kunkely, Horst

doi:10.1016/0022-328x(88)89005-3

Cited by 16 publications

(1 citation statement)

References 11 publications

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“…In a study of Hg[Co(CO) 4 ] 2 , it was noted that this compound exhibited an absorption band at 328 nm (ε ca. 25 000 L mol -1 cm -1 ), and this was assigned to a transition involving the linear Co−Hg−Co framework . The Hg−Co bonds in this species are polarized and exhibit Hg + −Co - character; thus, either a σ−σ* or d Co −σ* transition would have a significant component of Co → Hg charge transfer (MMCT) character.…”

Section: Discussionmentioning

confidence: 94%

Niobium−Mercury Heterometallic Compounds as Sources of Niobium(II): Radical Paths to Organoniobium Species

1997

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The niobium−mercury compounds [Cp‘2Nb(L)]2Hg (Cp‘ = η5-C5H4SiMe3, L = CO (4), PMe3 (5), or CNtBu (6)) serve as stable precursors to the short-lived Nb(II) radicals of general formula [Cp‘2Nb−L]. The homolysis of the Nb−Hg bond may result from a slow thermal reaction (generating low concentrations of radicals) or from a photochemical process in which mercury extrusion is more rapid. Since the Nb(II) species show no evidence for Nb−Nb bond formation, they are useful in the synthesis of a variety of Nb(III) and Nb(IV) species. Reactions of 4 with dimeric species such as [CpFe(CO)2]2, [CpNi(CO)]2, Co2(CO)8, or RSe−SeR give rise to new Nb−M or Nb−Se compounds, while reactions with potential π donors such as formaldehyde or azobenzene lead to displacement of the ligand L and formation of the Nb(IV) complexes. Crystallographic and variable-temperature NMR studies on the Nb−Fe compound Cp‘2Nb(μ-CO)2Fe(CO)Cp (10) are consistent with a low-energy fluxional process involving exchange of bridging and terminal carbonyl ligands.

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Section: Discussionmentioning

confidence: 94%

Niobium−Mercury Heterometallic Compounds as Sources of Niobium(II): Radical Paths to Organoniobium Species

1997

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Quecksilber, struktureller Baustein und Quelle lokalisierter Reaktivität in Metallclustern

Gade

1993

Angewandte Chemie

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Mercury, a Structural Building Block and Source of Localized Reactivity in Extended Metal–Metal Bonded Systems

Gade

1993

Angew. Chem. Int. Ed. Engl.

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Transition metal-mercury complexes were among the first compounds of study for the concept of direct metal-metal bonding which was established more than three decades ago. Since then, a large number of such systems have been synthesized and studied. The fact that mercury is readily attached to a large variety of main group or transition metals has stimulated its use as a general building block in the systematic synthesis of mixed-metal clusters. The past decade has witnessed a rapid expansion of b i m e t d k cluster chemistry in which species containing mercury have played a prominent role, and which has led to the discovery of many unprecedented cluster structures and reactions. In particular, the ability of mercury to form multicenter metal-metal bonds with polynuclear cluster fragments has substantially extended its coordination chemistry which was thus far dominated by simple linear structural arrangements. Although certain structural motifs are found to be common to many of the transition metalmercury clusters investigated to date and thus enable a relatively systematic synthetic approach, the multitude of surprising discoveries has kept the interest in the chemistry of the element itself alive. The recent discovery of the redox and photochemical reactivity of some of these systems has opened up an exciting and promising area of cluster research. Its significance for the synthetic methodology lies in the fact that the increasing redox activity of molecular carbonyl clusters on going to higher nuclearities appears to set a limit on the size of metal frameworks attainable by the standard preparative methods. On the other hand, their potential use as photochromes or redox mediaters in coupled electron-transfer reactions provides an additional stimulus for future studies in this field.

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Photochemistry of [MCo2(CO)8] (M = Zn, Cd, Hg) induced by metal to metal charge tranfer excitation

Cited by 16 publications

References 11 publications

Niobium−Mercury Heterometallic Compounds as Sources of Niobium(II): Radical Paths to Organoniobium Species

Niobium−Mercury Heterometallic Compounds as Sources of Niobium(II): Radical Paths to Organoniobium Species

Quecksilber, struktureller Baustein und Quelle lokalisierter Reaktivität in Metallclustern

Mercury, a Structural Building Block and Source of Localized Reactivity in Extended Metal–Metal Bonded Systems

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