Synthesis and Properties of Copper and Nickel Complexes of the General Formula (B11H11)2Mn-. Crystal Structure of [(n-Bu)4N]3[Cu(B11H11)2]

Kester, John G.; Keller, David L.; Huffman, John C.; Benefiel, M. A.; Geiger, William E.; Atwood, Christopher G.; Siedle, A. R.; Korba, Gary A.; Todd, Lee J.

doi:10.1021/ic00102a015

Cited by 28 publications

(17 citation statements)

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“…π sandwich and mixed-sandwich complexes exist for borane, monocarbaborane, and biscarbaborane cages, but again, the number of the latter examples is immensely superior. In particular, π complexes of boranes are quite rare: only a couple of Ni and Cu 1,1′-metalla- commo -bis(undecaborane) sandwich complexes and only a couple of Ni , and one Pd , mixed-sandwich closo -1-metalladodecaborane complexes have been structurally characterized (Figure ). Monocarbollide metal complexes with structures shown in Figure have been described, while to the best of our knowledge, none of the other possible isomers have been structurally described.…”

Section: Redox Behavior Of Boranes Carboranes and Metallacarboranesmentioning

confidence: 99%

Electrochemistry and Photoluminescence of Icosahedral Carboranes, Boranes, Metallacarboranes, and Their Derivatives

et al. 2016

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Icosahedral boranes, carboranes, and metallacarboranes are extraordinarily robust compounds with desirable properties such as thermal and redox stability, chemical inertness, low nucleophilicity, and high hydrophobicity, making them attractive for several applications such as medicine, nanomaterials, molecular electronics, energy, catalysis, environmental chemistry, and other areas. The hydrogen atoms in these clusters can be replaced by convenient groups that open the way to a chemical alternative to conventional "organic" or "organometallic" realms. Icosahedral boron cluster derivatives have been reviewed from different perspectives; however, there is a need for a review dedicated to the redox and photophysical characteristics of easily accessible borane and carborane derivatives, which are excellent materials for a wide range of applications. This review deals with the redox properties and photoluminescence behavior of this collection of compounds, as well as their influence on the properties of materials and devices whose working principles are related to electron-transfer or electron-promotion phenomena. We hope that this review will be of great value to boron cluster scientists and researchers working in the photoluminescence and electrochemistry fields who are interested in exploring the possibilities of these unique and promising systems.

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Section: Redox Behavior Of Boranes Carboranes and Metallacarboranesmentioning

confidence: 99%

Electrochemistry and Photoluminescence of Icosahedral Carboranes, Boranes, Metallacarboranes, and Their Derivatives

et al. 2016

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“…The past decade has seen an unusual surge of experimental and theoretical activities in cluster chemistry involving the icosahedron. − Recent developments in metal cluster chemistry, in particular, have resulted in a variety of metal clusters whose structures are based on an icosahedron. − The tendency of clusters to form the icosahedral structure may be termed “icosahedricity” 11m. An icosahedron can also serve as the basic building block for high-nuclearity metal clusters; for example, our recent work in this area gave rise to a series of bi- or trimetallic supraclusters whose metal framework can be described as vertex-sharing polyicosahedra 11 in which the 13-atom centered icosahedra are fused together via sharing of vertex atoms.…”

Section: Introductionmentioning

confidence: 99%

Iconography of Icosahedra. Calculations of Metallic Energies and Relative Stabilities of Stereoisomers of Binary Icosahedral Clusters

et al. 1998

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The first part of this paper provides a complete iconography of all possible stereoisomers of a binary icosahedron (a total of 96 for a noncentered A n B12- n (n = 0−12) and 192 for a centered A n B13- n (n = 0−13) icosahedron) by utilizing a simple symmetry-based algorithm. The second part of this paper deals with the relative stabilities of these stereoisomers for a given combination of A and B atoms. A simple theory, based on the Lennard-Jones potential and cohesive energies of transition metals, has been developed in order to model metallic bonding in a metal cluster. This provides a relative measure of the strengths of metal−metal bonds in a mixed-metal cluster and hence the relative energetic stabilities of various stereoisomers. The utility of this simple theory is illustrated by applying it to all possible stereoisomers of binary icosahedral clusters A n B13- n (n = 0−13) containing the Au−Ag, Au−Ni, and Au−Pt combinations. Considerable insight into metal−metal interactions in mixed-metal systems can be gained by detailed analysis of the contributionscovalent vs ionicto the metallic bonding energy. Indeed, on the basis of the calculated energies, two simple rulesthe Strong-Bond rule and the Hetero-Bond rulewere formulated. These rules are useful in predicting the relative stabilities of these stereoisomers, thereby furthering the understanding of site preference in multimetallic systems, including mixed-metal clusters, metal alloy systems, multimetallic catalysts, etc.

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“…In the past few years, we have investigated the use of the nido -borane cage ligand [B 11 H 11 ] 4- to support unusually high formal oxidation states of transition metals, such as Ni(IV) in [Ni(B 11 H 11 ) 2 ] 4- and Cu(V) in [Cu(B 11 H 11 ) 2 ] 3- . These complexes, along with the earlier [(C 5 H 5 )Ni(B 11 H 11 )] - anion, represent the only reported examples in which a nido -[B 11 H 11 ] 4- ligand bonds η 5 to a transition metal.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a Metallaborane Complex Containing Pd(III) and the First Doubly Charge Compensated Ollide Ion. X-ray Crystal Structure of 1,4-Br₂-1,2,5-(PMe₂Ph)₃-closo-1-PdB₁₁H₈

1998

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The reaction of [Me(3)NH][nido-B(11)H(14)] with 4 equiv of lithium alkyl in THF at 5 degrees C generated the putative ollide ion, Li(4)[B(11)H(11)], which was not isolated. This was treated in situ with (PMe(2)Ph)(2)PdBr(2) to yield the metallaborane 1,4-Br(2)-1,2,5-(PMe(2)Ph)(3)-closo-1-PdB(11)H(8). This metallaborane contains the first doubly charge compensated ollide ion. It was isolated in low yield from the reaction mixture by chromatography. Characterization of this air-stable palladium ollide complex by magnetic susceptibility, EPR, and CV confirmed that it contains Pd(III) and is paramagnetic. It was also characterized by an X-ray diffraction study of a single crystal. The sample consisted of rust-colored crystals of monoclinic space group P2(1)/c, with a = 9.749(13) Å, b = 16.30(2) Å, c = 21.65(3) Å, beta = 97.21(4) degrees, and Z = 4. The structure was determined by conventional heavy-atom methods and refined to a final value of R = 0.0730 (5172 reflections), R(w) = 0.0620.

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Synthesis and Properties of Copper and Nickel Complexes of the General Formula (B11H11)2Mn-. Crystal Structure of [(n-Bu)4N]3[Cu(B11H11)2]

Cited by 28 publications

References 1 publication

Electrochemistry and Photoluminescence of Icosahedral Carboranes, Boranes, Metallacarboranes, and Their Derivatives

Electrochemistry and Photoluminescence of Icosahedral Carboranes, Boranes, Metallacarboranes, and Their Derivatives

Iconography of Icosahedra. Calculations of Metallic Energies and Relative Stabilities of Stereoisomers of Binary Icosahedral Clusters

Synthesis of a Metallaborane Complex Containing Pd(III) and the First Doubly Charge Compensated Ollide Ion. X-ray Crystal Structure of 1,4-Br₂-1,2,5-(PMe₂Ph)₃-closo-1-PdB₁₁H₈

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Synthesis and Properties of Copper and Nickel Complexes of the General Formula (B11H11)2Mn-. Crystal Structure of [(n-Bu)4N]3[Cu(B11H11)2]

Cited by 28 publications

References 1 publication

Electrochemistry and Photoluminescence of Icosahedral Carboranes, Boranes, Metallacarboranes, and Their Derivatives

Electrochemistry and Photoluminescence of Icosahedral Carboranes, Boranes, Metallacarboranes, and Their Derivatives

Iconography of Icosahedra. Calculations of Metallic Energies and Relative Stabilities of Stereoisomers of Binary Icosahedral Clusters

Synthesis of a Metallaborane Complex Containing Pd(III) and the First Doubly Charge Compensated Ollide Ion. X-ray Crystal Structure of 1,4-Br2-1,2,5-(PMe2Ph)3-closo-1-PdB11H8

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Synthesis of a Metallaborane Complex Containing Pd(III) and the First Doubly Charge Compensated Ollide Ion. X-ray Crystal Structure of 1,4-Br₂-1,2,5-(PMe₂Ph)₃-closo-1-PdB₁₁H₈