Bond, bridge valence

The parent thionine system 1 up to now has not been prepared probably because the C-S bond in valence isomeric forms is too weak giving rise to facile rearrangement or decomposition. The obvious synthetic route, photochemical transformation of cyclooctatetraenccpisulfide 2 (9-thiabicyclo[6.1.0]nona-2,4,6-triene), does not lead to 1, but intriguingly to another valence isomer, the sulfur-bridged homotropylidene system 3.20... 

Tetranuclear monoadducts with asymmetrical M- O M bridges related to those of [M2OCI9] have been characterized but most structural data concern monomeric NbOCls bis adducts. In such derivatives, the metal is octahedrally surrounded with the neutral Ugands cis to each other, one being trans to the 0x0 bond, which is short (typical Nb=0 Bond Length 1.70 A). The coordination polyhedron is distorted as a result of the niobium-oxygen multiple bond (see Valence Shell Electron Pair Repulsion Model). ... 

The nature of the chemical bond bridges the structures and properties of crystals and molecules [1]. Interatomic interaction and electronic distribution in the valence band are the keys to engineering materials. The spontaneous bond contraction enhances the binding energy of the remaining bonds of the lower coordinated atom. Chemical reaction modifies directly the occupied valence DOS by charge transportation or polarization. Bond relaxation and valence band modulation change the properties of a solid. 

Localized Bonds. Because boron hydrides have more valence orbitals than valence electrons, they have often been called electron-deficient molecules. This electron deficiency is partiy responsible for the great interest surrounding borane chemistry and molecular stmcture. The stmcture of even the simplest boron hydride, diborane(6) [19287-45-7] 2 6 sufficientiy challenging that it was debated for years before finally being resolved (57) in favor of the hydrogen bridged stmcture shown. 

Structure. The CO molecule coordinates in the ways shown diagrammaticaHy in Figure 1. Terminal carbonyls are the most common. Bridging carbonyls are common in most polynuclear metal carbonyls. As depicted, metal—metal bonds also play an important role in polynuclear metal carbonyls. The metal atoms in carbonyl complexes show a strong tendency to use ak their valence orbitals in forming bonds. These include the n + 1)5 and the n + l)p orbitals. As a result, use of the 18-electron rule is successflil in predicting the stmcture of most metal carbonyls. 

The boranes are electron-deficient compounds (Section 3.8) we cannot write valid Lewis structures for them, because too few electrons are available. For instance, there are 8 atoms in diborane, so we need at least 7 bonds however, there are only 12 valence electrons, and so we can form at most 6 electron-pair bonds. In molecular orbital theory, these electron pairs are regarded as delocalized over the entire molecule, and their bonding power is shared by several atoms. In diborane, for instance, a single electron pair is delocalized over a B—H—B unit. It binds all three atoms together with bond order of 4 for each of the B—H bridging bonds. The molecule has two such bridging three-center bonds (9). 

The Mn C [Mn6(OH)3Cl3(hmp)9]6 2+ (31) complex, where hmp is 2-hydroxymethylpyridine, is structurally very close to these two manganese rings. It is a mixed-valence manganese cluster with a central Mn2+ ion. A Cl- counterion is hydrogen-bonded to the p3-OH groups which bridge the six Mn ions. 

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