Mechanistic features of metal cluster rearrangements

Band, Elliot I.; Muetterties, E. L.

doi:10.1021/cr60316a003

Cited by 161 publications

(67 citation statements)

References 38 publications

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“…2). In fact, the dianionic cluster exhibited only two equal-intensity '3C CO resonances from +200C to -900C, which is most realistically explained by a fast CO site exchange localized on individual iron atoms, a process commonly observed (15) for metal carbonyl clusters (Fig. 3).…”

mentioning

confidence: 82%

Structure and chemistry of a metal cluster with a four-coordinate carbide carbon atom

Davis

Beno

Williams

et al. 1981

Proc. Natl. Acad. Sci. U.S.A.

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confidence: 82%

Structure and chemistry of a metal cluster with a four-coordinate carbide carbon atom

Davis

Beno

Williams

et al. 1981

Proc. Natl. Acad. Sci. U.S.A.

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“…On the basis of their relative intensities, it can be roughly inferred that the equilibrium constant for the interconversion in Equation (5) À results in a decreased volume of the anion, because of significant shortening of the CO support- [ It is widely accepted that energy barrier for the terminalbridge interconversion of the CO ligands is low, as deduced from the easy scrambling processes of several carbonyl compounds on the 13 C NMR timescale. [30] It is now shown that such interconversion can be promoted by packing forces. 16 ]Cl has been measured and the results are collated in Table 5.…”

Section: The Relevant Bond Lengths Observed For the Ethylviologen In mentioning

confidence: 99%

New Hybrid Semiconductor Materials Based on Viologen Salts of Bimetallic Fe–Pt and Fe–Au Carbonyl Clusters: First Structural Characterization of the Diradical π‐Dimer of the Diethylviologen Monocation and EPR Evidence of its Triplet State

Femoni

Iapalucci

Longoni

et al. 2007

Chemistry A European J

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The synthesis, structure, spectroscopic characterization and electrical resistivity of the [EtV](2)[Fe(4)Pt(CO)(16)], [EtV][Fe(3)Pt(3)(CO)(15)].THF, [EtV][Fe(4)Au(CO)(16)](2)2.THF (EtV=1,1'-diethyl-4,4'-bipyridilium cation) and [NEt(4)](2)[Fe(4)Au(CO)(16)] is reported. The crystal structure of [EtV](2)[Fe(4)Pt(CO)(16)] is based on infinite stacks of [(EtV)(*+)](2) pi-dimers rotated by 90 degrees and isolated [Fe(4)Pt(CO)(16)](2-) ions. Within each pi-dimer, the [EtV](*+) radical ions are perfectly eclipsed and the distance between their mean planes is 3.275 A. The EPR spectrum of the solid material at room temperature clearly indicates the presence of a significantly populated triplet state of the pi-dimer, by showing signals both at Deltam=1 and Deltam=2. The solid-state structure of [EtV][Fe(3)Pt(3)(CO)(15)].THF is based on the ionic packing of [EtV](2+) and [Fe(3)Pt(3)(CO)(15)](2-) ions, inferred from a comparison of their molecular parameters with literature data. Significant electron transfer could have been expected to give [EtV](*+)[Fe(3)Pt(3)(CO)(15)](*-) on the basis of their formal redox potentials. In spite of their different stoichiometries, the structures of [EtV][Fe(4)Au(CO)(16)](2).2 THF and [NEt(4)](2)[Fe(4)Au(CO)(16)] both contain an isomer of the monoanion [Fe(4)Au(CO)(16)](-) in solution (previously characterized in the solid state as a [NMe(3)CH(2)Ph](2)[Fe(4)Au(CO)(16)]Cl mixed salt). Resistivity measurements on pellets of powdered samples of the above compounds indicate that their tetrasubstituted ammonium salts, and complex [EtV][Fe(4)Au(CO)(16)](2)2.THF, largely behave as insulators. However, the [EtV](2)[Fe(4)Pt(CO)(16)] and [EtV][Fe(3)Pt(3)(CO)(15)].THF samples respectively display resistivities 3 and 4 orders of magnitude less than those of their corresponding ammonium salts and could be classified as semiconductor materials.

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“…The extraordinary geometrical versatility shown by CO is demonstrated in the results of scores of structural studies on metal carbonyl complexes and clusters both in solution and in the solid state (Band & Muetterties, 1978;Evans, 1977). As a matter of fact, while spectroscopic techniques have provided most information on the dynamic processes related to CO fluxionality in solution (Adams & Cotton, 1985), thus far solid-state aspects of CO structural chemistry mainly have been investigated by single-crystal X-ray and neutron diffraction (Raithby, 1980).…”

Section: Introductionmentioning

confidence: 99%

A mean-square displacement amplitude analysis of terminally bound CO groups in transition-metal clusters

Braga¹,

Koetzle²

1988

Acta Crystallogr Sect B

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Mean-square displacement amplitudes (m.s.d.a.'s) obtained from conventional room-temperature and low-temperature X-ray diffraction, and from neutron diffraction studies of metal carbonyl clusters are analyzed for the terminally bound CO groups. The relationships between m.s.d.a.'s of M, C and O atoms are investigated by applying the 'rigid-body' test along the M--C, M--O and C-O vectors, and are examined on the basis of simple vibrational motion models. Results of this analysis show that the C-atom m.s.d.a.'s are substantially affected by bonding electron density deformation. The relationship with the 'sliding effect' observed on passing from isotropic to anisotropic treatment of the C-atom thermal motion is also discussed.

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Mechanistic features of metal cluster rearrangements

Cited by 161 publications

References 38 publications

Structure and chemistry of a metal cluster with a four-coordinate carbide carbon atom

Structure and chemistry of a metal cluster with a four-coordinate carbide carbon atom

New Hybrid Semiconductor Materials Based on Viologen Salts of Bimetallic Fe–Pt and Fe–Au Carbonyl Clusters: First Structural Characterization of the Diradical π‐Dimer of the Diethylviologen Monocation and EPR Evidence of its Triplet State

A mean-square displacement amplitude analysis of terminally bound CO groups in transition-metal clusters

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