Boron coordination number

The oxygen to boron ratio of the metaborates (2 1) requires that at least one of the oxygen atoms must be shared between two boron atoms to obtain the customary boron coordination number. Metaborates with the triangular BO3 group crystallize in (a) a trimeric ring structure, or (h) a chain structure. Sodium and potassium metaborates and orthorhombic... 

The melting and boiling points of the aluminium halides, in contrast to the boron compounds, are irregular. It might reasonably be expected that aluminium, being a more metallic element than boron, would form an ionic fluoride and indeed the fact that it remains solid until 1564 K. when it sublimes, would tend to confirm this, although it should not be concluded that the fluoride is, therefore, wholly ionic. The crystal structure is such that each aluminium has a coordination number of six, being surrounded by six fluoride ions. 

R. E. Williams, Coordination number-pattern recognition theory of carborane structures, Adv. Incrg. Chem. Radiochem. 18, 67-142 (1976). R. E. Williams, Chap. 2 in G. A. Olah, K. Wade and R. E. Williams (eds.). Electron Deficient Boron and Carbon Clusters, Wiley, New York, 1991, pp. 11-93. 

Boron-boron distances in the cluster increase with increasing coordination number (as expected). Average B-B distances are 5-coordinate B 170pm, 6-coordinate B 177pm, 7-coordinate B 186pm. 

The radius ratio for B+3 is only a little less than the lower limit for tetra-hedra. The usual coordination number for boron with oxygen is 3 (in the borate ion, [B03]-3). It is four, however, in the 12-tungstoborate ion,16 in which a stabilizing influence is exerted by the tungsten octahedra. 

Table 8.4 Bond Length and Coordination Number in the Chlorides, Fluorides, and Hydrides of Boron and Carbon...

Cubed compound, in PVC siding manufacture, 25 685 Cube lattice, 8 114t Cubic boron nitride, 1 8 4 654 grinding wheels, 1 21 hardness in various scales, l 3t physical properties of, 4 653t Cubic close-packed (CCP) structure, of spinel ferrites, 11 60 Cubic ferrites, 11 55-57 Cubic geometry, for metal coordination numbers, 7 574, 575t. See also Cubic structure Cubic symmetry Cubic silsesquioxanes (CSS), 13 539 Cubic structure, of ferroelectric crystals, 11 94-95, 96 Cubic symmetry, 8 114t Cubitron sol-gel abrasives, 1 7 Cucurbituril inclusion compounds,... 

The case of boron as a network former cation is somewhat specific in that this element has no available d orbitals. However, a p orbital is available when the boron has a coordination number of 3, which allows stabilisation of an electronic doublet of the oxygen or sulphur introduced by the modifier. This oxygen or sulphur giving up a doublet to another boron atom increases the cross-linking by the formation of two BO4 tetrahedra. In hybridisation terms, the boron is altered from the sp configuration to the sp configuration. The coordination change of boron has been especially well observed by NMR (Bray and O Keefe, 1963 Muller-Warmuth and Eckert, 1982). 

The C—C and C—B interatomic distances in carboranes can also be related to the coordination numbers of the skeletal atoms. Two factors tend to make these distances shorter than the B —B distances in comparable boranes the preference of the carbon atoms for sites of low coordination number and the greater electronegativity of carbon than boron, which increases the electron density in the region of the carbon atoms and so strengthens the bonds that they form. Table IX lists some C—C distances for closo- and wido-carboranes 13, 20, 21, 26, 98,121,168) and metal-acetylene 50, 58,112) complexes, relating them... 

The structures, relative stabilities, and relative Lowry-Bronsted acidities of carboranes and boranes as well as related anions, Lewis base adducts, and heteroelement analogs are rationalized primarily on the basis of rudimentary coordination numbers. The principal factors, in decreasing order of importance, are (a) the various deltahedra and deltahedral fragments, (b) the placement of bridge and endohydrogens, (c) the placement of carbon and other heteroelements, and d) the resulting coordination number of boron. 

In systems derived from PH3 BH3, changes in the coupling constant, /pH, are found which are similar to those seen in compounds derived from PH3, i.e. compounds with phosphorus in coordination number 3. The observation that the alteration does not correspond to that seen for derivatives of PHi suggests that the very weak donor-acceptor bond in PH3 BH3 does not affect the hybridisation of phosphorus, as compared with that in free PH3, as much as might at first be expected. A small increase in the electron withdrawing action by halogen substitution of the hydrogen atoms bonded to boron causes an increase in the s character of the P-H bonds. 

Fluorine complexes behave in the same way. Boron, in the first period, still does not show the normal coordination number and only forms BF, while the larger aluminium ion forms Na3AlF6 with a higher coordination number. The carbon ion in CF4 is, however, so small that the coordination number is limited to four and complex formation is completely absent. On the other hand, the larger Si4+ ion gives normal complexes such as K2SiF6, etc. 

Gmelin Handbook Volumes on Boron and its Compounds (a) Main Volume (1926) (b) Supplement vol. 1 (1954) (c) Compounds 8 (NSSV 33), The tetrahydroborate ion and its derivatives (1976) (d) Compounds 9 (NSSV 34), Boron-halogen compounds , Part 1 (1976) (e) Compounds 10 (NSSV 37), Boron compounds with coordination number 4 (1976) (f) Compounds 15 (NSSV 46), Amine-boranes (1977) (g) Compounds 19 (NSSV 53), Boron-halogen compounds , Part 2 (1978) (h) Supplement Volumes (1980-82), Springer-Verlag, Berlin. 

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