Heteroborane
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Heteroborane
Heteroboranes are classes of boranes, at least one boron atom is replaced by another element. Like many of the related boranes, these clusters are polyhedra and are similarly classified as ''closo-, nido-, arachno-, hypho-,'' according to the so-called electron count. ''Closo-'' represents a complete polyhedron, while ''nido-'', ''arachno-'' and ''hypho-'' stand for polyhedrons that are missing one, two and three vertices. Structurally, various heteroboranes can be derived from the icosahedral (''I''h) B12H122– via formal replacement of its BH fragments with isoelectronic CH+, P+ or S2+ fragments, e.g. ''closo''-1-CB11H12–, ''closo''-1,2-C2B10H12, ''closo''-1,2-P2B10H10 or ''closo''-1-SB11H11. See also * Carborane * Azaborane Azaborane usually refers a boranes, borane Cluster chemistry, cluster where BH vertices are replaced by N or NR (R = H, organic substituent). Like many of the related boranes, these clusters are polyhedra and can be classified as ''closo-'', ''nid . ...
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Carborane
Carboranes are electron-delocalized (non-classically bonded) clusters composed of boron, carbon and hydrogen atoms.Grimes, R. N., ''Carboranes 3rd Ed.'', Elsevier, Amsterdam and New York (2016), . Like many of the related boron hydrides, these clusters are polyhedra or fragments of polyhedra. Carboranes are one class of heteroboranes. In terms of scope, carboranes can have as few as 5 and as many as 14 atoms in the cage framework. The majority have two cage carbon atoms. The corresponding C-alkyl and B-alkyl analogues are also known in a few cases. Structure and bonding Carboranes and boranes adopt 3-dimensional cage (cluster) geometries in sharp contrast to typical organic compounds. Cages are compatible with sigma—delocalized bonding, whereas hydrocarbons are typically chains or rings. Like for other electron-delocalized polyhedral clusters, the electronic structure of these cluster compounds can be described by the Wade–Mingos rules. Like the related boron hydrides, th ...
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Boranes
Boranes is the name given to compounds with the formula BxHy and related anions. Many such boranes are known. Most common are those with 1 to 12 boron atoms. Although they have few practical applications, the boranes exhibit structures and bonding that differs strongly from the patterns seen in hydrocarbons. Hybrids of boranes and hydrocarbons, the carboranes are also well developed. History The development of the chemistry of boranes led to innovations in synthetic methods as well as structure and bonding. First, new synthetic techniques were required to handle diborane and many of its derivatives, which are both pyrophoric and volatile. Alfred Stock invented the glass vacuum line for this purpose. The structure of diborane was correctly predicted in 1943 many years after its discovery. The structures of the boron hydride clusters were determined beginning in 1948 with the characterization of decaborane. William Lipscomb was awarded the Nobel prize in Chemistry in 1976 for th ...
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Boron
Boron is a chemical element with the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the ''boron group'' it has three valence electrons for forming covalent bonds, resulting in many compounds such as boric acid, the mineral borax, sodium borate, and the ultra-hard crystals of boron carbide and boron nitride. Boron is synthesized entirely by cosmic ray spallation and supernovae and not by stellar nucleosynthesis, so it is a low-abundance element in the Solar System and in the Crust (geology), Earth's crust. It constitutes about 0.001 percent by weight of Earth's crust. It is concentrated on Earth by the water-solubility of its more common naturally occurring compounds, the borate minerals. These are mined industrially as evaporites, such as borax and kernite. The largest known deposits are in Turkey, the largest producer of boron minerals. Elemental b ...
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Polyhedra
In geometry, a polyhedron (plural polyhedra or polyhedrons; ) is a three-dimensional shape with flat polygonal faces, straight edges and sharp corners or vertices. A convex polyhedron is the convex hull of finitely many points, not all on the same plane. Cubes and pyramids are examples of convex polyhedra. A polyhedron is a 3-dimensional example of a polytope, a more general concept in any number of dimensions. Definition Convex polyhedra are well-defined, with several equivalent standard definitions. However, the formal mathematical definition of polyhedra that are not required to be convex has been problematic. Many definitions of "polyhedron" have been given within particular contexts,. some more rigorous than others, and there is not universal agreement over which of these to choose. Some of these definitions exclude shapes that have often been counted as polyhedra (such as the self-crossing polyhedra) or include shapes that are often not considered as valid polyhed ...
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Polyhedral Skeletal Electron Pair Theory
In chemistry the polyhedral skeletal electron pair theory (PSEPT) provides electron counting rules useful for predicting the structures of clusters such as borane and carborane clusters. The electron counting rules were originally formulated by Kenneth Wade, and were further developed by others including Michael Mingos; they are sometimes known as Wade's rules or the Wade–Mingos rules. The rules are based on a molecular orbital treatment of the bonding. These notes contained original material that served as the basis of the sections on the 4''n'', 5''n'', and 6''n'' rules. These rules have been extended and unified in the form of the Jemmis ''mno'' rules. Predicting structures of cluster compounds Different rules (4''n'', 5''n'', or 6''n'') are invoked depending on the number of electrons per vertex. The 4''n'' rules are reasonably accurate in predicting the structures of clusters having about 4 electrons per vertex, as is the case for many boranes and carboranes. For such ...
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Dodecaborate
The dodecaborate(12) anion, 12H12sup>2−, is a borane with an icosahedral arrangement of 12 boron atoms, with each boron atom being attached to a hydrogen atom. Its symmetry is classified by the molecular point group Ih. Synthesis and reactions The existence of the dodecaborate(12) anion, 12H12sup>2−, was predicted by H. C. Longuet-Higgins and M. de V. Roberts in 1955. Hawthorne and Pitochelli first made it 5 years later, by the reaction of 2-iododecaborane with triethylamine in benzene solution at 80 °C. It is more conveniently prepared in two steps from sodium borohydride. First the borohydride is converted into a triborate anion using the etherate of boron trifluoride: : 5 NaBH4 + BF3 → 2 NaB3H8 + 3 NaF + 2 H2 Pyrolysis of the triborate gives the twelve-boron cluster as the sodium salt. A variety of other synthetic methods have been published. Salts of the dodecaborate ion are stable in air and do not react with hot aqueous sodium hydroxide or hydrochloric acid. ...
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Azaborane
Azaborane usually refers a boranes, borane Cluster chemistry, cluster where BH vertices are replaced by N or NR (R = H, organic substituent). Like many of the related boranes, these clusters are polyhedra and can be classified as ''closo-'', ''nido-'', ''arachno-'', etc. Within the context of Polyhedral skeletal electron pair theory, Wade's rules, NR is a 4-electron vertex, and N is a 3-electron vertex. Prominent examples are the charge-neutral ''nido''-NB10H13 (i.e. (NH)(BH)10) and ''closo''-NB11H12 (i.e. (NH)(BH)11).{{cite journal, author=P. Paetzold, title=New Perspectives in Boron-Nitrogen Chemistry-I, year=1991, pages=345–350, volume=63, journal=Pure Appl. Chem., issue=3, doi=10.1351/pac199163030345, s2cid=53659373, url=https://www.iupac.org/publications/pac/pdf/1991/pdf/6303x0345.pdf Azaboranes can also refer to simpler compounds including iminoboranes (formula = RN=NR') and borazines. See also * Carborane References Boron–nitrogen compounds Cluste ...
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Boron Compounds
Boron compounds are compounds containing the element boron. In the most familiar compounds, boron has the formal oxidation state +3. These include oxides, sulfides, nitrides, and halides. Halides The trihalides adopt a planar trigonal structure. These compounds are Lewis acids in that they readily form adducts with electron-pair donors, which are called Lewis bases. For example, fluoride (F−) and boron trifluoride (BF3) combined to give the tetrafluoroborate anion, BF4−. Boron trifluoride is used in the petrochemical industry as a catalyst. The halides react with water to form boric acid. Boron is found in nature on Earth almost entirely as various oxides of B(III), often associated with other elements. More than one hundred borate minerals contain boron in oxidation state +3. These minerals resemble silicates in some respect, although boron is often found not only in a tetrahedral coordination with oxygen, but also in a trigonal planar configuration. Unlike silicates, b ...
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Cluster Chemistry
In chemistry, an atom cluster (or simply cluster) is an ensemble of bound atoms or molecules that is intermediate in size between a simple molecule and a nanoparticle; that is, up to a few nanometers (nm) in diameter. The term ''microcluster'' may be used for ensembles with up to couple dozen atoms. Clusters with a definite number and type of atoms in a specific arrangement are often considered a specific chemical compound and are studied as such. For example, fullerene is a cluster of 60 carbon atoms arranged as the vertices of a truncated icosahedron, and decaborane is a cluster of 10 boron atoms forming an incomplete icosahedron, surrounded by 14 hydrogen atoms. The term is most commonly used for ensembles consisting of several atoms of the same element, or of a few different elements, bonded in a three-dimensional arrangement. Transition metals and main group elements form especially robust clusters. Indeed, in some contexts, the term may refer specifically to a metal cl ...
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