The Interface of Main Group and Transition Metal Cluster Chemistry

Whitmire, Kenton H.

doi:10.1080/00958978808075858

Cited by 206 publications

(17 citation statements)

References 391 publications

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“…The carbide atom is located below the iron basal mean plane, the distance from this plane being 0.13 Å, which lies between that found for the clusters [Fe 5 C(CO) 15 ] (0.09 Å) and [Fe 5 C(CO) 14 ] 2- (0.18 Å). This distance is a measure of the negative charge on the carbon carbide atom . This feature has also been observed for the homologous osmium clusters [Os 5 C(CO) 15 ] and [Os 5 C(CO) 14 ] 2- as well as for the series of ruthenium derivatives [Ru 5 C(CO) 15 - x (PPh 3 ) x ]. − The average distance between the carbide and the basal iron atoms is 1.88 Å, appreciably shorter than that of 1.967 Å observed for C−Fe 5 (apical).…”

Section: Resultsmentioning

confidence: 56%

Electrophilic Additions of Mercury and Gold Species to the Anion Carbide Cluster [Fe₅C(CO)₁₄]²^-. X-ray Crystal Structures of (NEt₄)[Fe₅C(CO)₁₄{μ-HgW(CO)₃Cp}] and (NEt₄)₂[μ₄-Hg{Fe₅C(CO)₁₄}₂]

et al. 1998

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The reaction of the carbide carbon anion [Fe5C(CO)14]2- with ClHgM in tetrahydrofuran gives the new heptametallic clusters (NEt4)[Fe5C(CO)14{μ-HgM}] (M = Mo(CO)3Cp (1a), W(CO)3Cp (1b), Mn(CO)5 (1c), Co(CO)4 (1d), Fe(CO)2Cp (1e)). The spiro species (NEt4)2[μ4-Hg{Fe5C(CO)14}2] (2) has been isolated by reaction of the pentairon carbide carbon dianion with Hg(NO3)2. The structures of 1b and 2 have been determined by X-ray diffraction methods. The anion of 1b has an Fe5 square-pyramidal metal skeleton in which a basal edge is bridged by the HgW(CO)3Cp moiety. For the cluster anion 2, the metal core consists of a four-coordinate mercury atom bridging the bond edges of two square-based-pyramidal pentairon units. The electrochemical behavior of these compounds has been investigated by cyclic voltammetry and coulometry. The 57Fe Mössbauer spectroscopy of complexes 1b,e reveals the existence of three and four types of iron sites, respectively. This study has been extended by reacting the new species (NEt4)[Fe5C(CO)14{μ-HgM}] (1a,b) with AuPPh3 + to give the neutral octametallic clusters [Fe5C(CO)14{μ-HgM}{μ-AuPPh3}] (M = Mo(CO)3Cp (3a), W(CO)3Cp (3b)).

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Section: Resultsmentioning

confidence: 56%

Electrophilic Additions of Mercury and Gold Species to the Anion Carbide Cluster [Fe₅C(CO)₁₄]²^-. X-ray Crystal Structures of (NEt₄)[Fe₅C(CO)₁₄{μ-HgW(CO)₃Cp}] and (NEt₄)₂[μ₄-Hg{Fe₅C(CO)₁₄}₂]

et al. 1998

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“…Main-group heteroatoms in organometallic cluster compounds are generally found either in an interstitial position or on the periphery as a part of the cluster skeleton, depending on the type of heteroatom. Naked C and N atoms prefer the interstitial position, while oxo, sulfide, and, in some cases, nitride ligands can be found as a peripheral component of the clusters.…”

mentioning

confidence: 99%

“…Organometallic clusters containing the oxo ligand are much less numerous than organometallic carbides, nitrides, and sulfides though there are many examples of such oxo ligands in polyoxometalates and metallic oxo clusters .…”

mentioning

confidence: 99%

Penta- and Hexanuclear Heterometallic Carbonyl Clusters with μ₃-O Ligands

Полякова¹,

Губин²,

Belyakova³

et al. 1997

Organometallics

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The trigonal-bipyramidal [Fe3Au2(CO)12(PPh3)2(μ3-O)] and octahedral [Fe3Rh3(CO)15(μ3-O)]- clusters have been obtained from the reaction between a triangular [Fe3(CO)9(μ3-O)]2- cluster and metal-containing compounds Au(PPh3)X (X = Cl, NO3) and [Rh(CO)2Cl]2, respectively. X-ray structural studies revealed that the addition of two Au(PPh3) or three Rh(CO)2 groups to [Fe3(CO)9(μ3-O)]2- resulted in clusters with a virtually unchanged Fe3(μ3-O) fragment.

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“…1,2 Transition metals in the form of the cluster are of great interest due to their structural diversity and potential applications in the field of catalysis and material science. 3,4 Earlier reports account for two transition metal oxides, namely titanium dioxide and zinc oxide (TiO 2 and ZnO), as a versatile catalyst due to their enormous applications such as in the removal of organic pollutants and as a catalyst in various fields like electrochemistry, [5][6][7] photochemical energy conversion, 8,9 CO hydrogenation reactions, [10][11][12][13] self-cleaning tiles, glasses, as well as day-to-day life products like food and personal care products. [14][15][16][17] Above-mentioned applications encouraged us to utilize metal oxide clusters, such as TiO 2 and ZnO, as a catalyst in the study of degradation reaction.…”

Section: Introductionmentioning

confidence: 99%

ZnO and TiO₂ clusters as catalyst in the addition and abstraction reaction of acrylic acid with the OH radical

Aazaad

Lakshmipathi

2019

Int J of Chemical Kinetics

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The present work displays the theoretical analysis on the role of metal oxide clusters as an effective catalyst in the reaction between acrylic acid and OH radical, which has an energy barrier of 12.4 kcal/mol. The formation of metal oxide cluster such as ZnO and TiO2 with varying size from monomer to hexamer is analyzed using cohesive energy, which increases with cluster size. Adsorption of acrylic acid on clusters reveals that dimer ZnO and tetramer TiO2 are good adsorbed entities. The dimer ZnO and tetramer TiO2 clusters have reduced the barrier height. However, from the thermodynamical analysis of H‐abstraction and OH addition reaction, the dimer ZnO cluster is found to be a good catalyst than a tetramer TiO2 cluster. The favorable H abstraction and OH addition reactions are feasible at the active methylene group (–CH). OH addition reactions dominate over the H abstraction reaction. Further, the presence of metal oxide clusters enhances the rate of the reaction between acrylic acid and OH radical. The kinetics of the favorable reaction with a dimer ZnO cluster has a rate constant of 7.80 × 10−11 cm3 molecule−1 s−1, which is higher than the literature report (1.75 × 10−11 cm3 molecule−1 s−1). Overall, ZnO and TiO2 metal oxide clusters can be effectively utilized as catalyst.

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The Interface of Main Group and Transition Metal Cluster Chemistry

Cited by 206 publications

References 391 publications

Electrophilic Additions of Mercury and Gold Species to the Anion Carbide Cluster [Fe₅C(CO)₁₄]²^-. X-ray Crystal Structures of (NEt₄)[Fe₅C(CO)₁₄{μ-HgW(CO)₃Cp}] and (NEt₄)₂[μ₄-Hg{Fe₅C(CO)₁₄}₂]

Electrophilic Additions of Mercury and Gold Species to the Anion Carbide Cluster [Fe₅C(CO)₁₄]²^-. X-ray Crystal Structures of (NEt₄)[Fe₅C(CO)₁₄{μ-HgW(CO)₃Cp}] and (NEt₄)₂[μ₄-Hg{Fe₅C(CO)₁₄}₂]

Penta- and Hexanuclear Heterometallic Carbonyl Clusters with μ₃-O Ligands

ZnO and TiO₂ clusters as catalyst in the addition and abstraction reaction of acrylic acid with the OH radical

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The Interface of Main Group and Transition Metal Cluster Chemistry

Cited by 206 publications

References 391 publications

Electrophilic Additions of Mercury and Gold Species to the Anion Carbide Cluster [Fe5C(CO)14]2-. X-ray Crystal Structures of (NEt4)[Fe5C(CO)14{μ-HgW(CO)3Cp}] and (NEt4)2[μ4-Hg{Fe5C(CO)14}2]

Electrophilic Additions of Mercury and Gold Species to the Anion Carbide Cluster [Fe5C(CO)14]2-. X-ray Crystal Structures of (NEt4)[Fe5C(CO)14{μ-HgW(CO)3Cp}] and (NEt4)2[μ4-Hg{Fe5C(CO)14}2]

Penta- and Hexanuclear Heterometallic Carbonyl Clusters with μ3-O Ligands

ZnO and TiO2 clusters as catalyst in the addition and abstraction reaction of acrylic acid with the OH radical

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Electrophilic Additions of Mercury and Gold Species to the Anion Carbide Cluster [Fe₅C(CO)₁₄]²^-. X-ray Crystal Structures of (NEt₄)[Fe₅C(CO)₁₄{μ-HgW(CO)₃Cp}] and (NEt₄)₂[μ₄-Hg{Fe₅C(CO)₁₄}₂]

Electrophilic Additions of Mercury and Gold Species to the Anion Carbide Cluster [Fe₅C(CO)₁₄]²^-. X-ray Crystal Structures of (NEt₄)[Fe₅C(CO)₁₄{μ-HgW(CO)₃Cp}] and (NEt₄)₂[μ₄-Hg{Fe₅C(CO)₁₄}₂]

Penta- and Hexanuclear Heterometallic Carbonyl Clusters with μ₃-O Ligands

ZnO and TiO₂ clusters as catalyst in the addition and abstraction reaction of acrylic acid with the OH radical