PSEPT polyhedral skeletal electron pair

H2OEP = Octaethylporphyrin PPN = Bis(triphenylphos-phino)immium(l+) PSEPT = Polyhedral skeletal electron pair theory TMEDA = Af,Af,A, A -Tetramethylethylene-diamine nbd = Norbomadiene cod = 1,5-Cyclooctadiene. 

DFT = Density Functional Theory DSD = Diamond-Square-Diamond HOMO = Highest Occupied Molecular Orbital IR = Irreducible Representation LCAO = Linear Combination of Atomic Orbitals Ph = Phenyl PSEPT = Polyhedral Skeletal Electron Pair Theory SCF = Self-Consistent-Field SDDS = Square-Diamond, Diamond-Square TSH = Tensor Surface Harmonic. 

PSEPT Polyhedral skeletal electron pair theory... 

The following optimum electron numbers have been defined on the basis of the so-called Polyhedral Skeletal Electron-Pair Theory (PSEPT) . 

A particularly useful tool is the Polyhedral Skeletal Electron Pair Theory (PSEPT),3 originated by K. Wade, elaborated by D. M. P. Mingos and others, and known colloquially as Wade s Rules. This approach and its applications to carbocations, metal clusters, and other non-boron species, are described in numerous books and reviews. Here we simply outline the basic rules. 

A theory which shows greater applicability to bonding in cluster compounds is the Polyhedral Skeletal Electron Pair Theory (PSEPT) which allows the probable structure to be deduced from the total number of skeletal bond pairs (400). Molecular orbital calculations show that a closed polyhedron with n vertex atoms is held together by a total of (n + 1) skeletal bond pairs. A nido polyhedron, with one vertex vacant, is held together by (n + 2) skeletal bond pairs, and an arachno polyhedron, with two vacant vertices, by (n + 3) skeletal bond pairs. Further, more open structures are obtainable by adding additional pairs of electrons. This discussion of these polyhedral shapes is normally confined to metal atoms, but it is possible to consider an alkyne, RC=CR, either as an external ligand or as a source of two skeletal CR units. So that, for example, the cluster skeleton in the complex Co4(CO)10(RCCR), shown in Fig. 16, may be considered as a nido trigonal bipyramid (a butterfly cluster) with a coordinated alkyne or as a closo octahedron with two carbon atoms in the core. 

The polyhedral structures adopted by most metallacarbab-orane compounds can usually be rationalized using polyhedral skeletal electron pair theory (PSEPT) (see Electronic Structure of Clusters). This approach is summarized as follows ... 

It became necessary to develop new approaches for predicting electron closed-shell structures, and ideas came from Williams, Wade, Mingos, and Rudolph, which now make up the polyhedral skeletal electron pair theory (PSEPT). The bonding in clusters can sometimes be described in terms of edge-localized, two-center two-electron bonds. Thus, through the formation of element-element bonds, the atoms of a polyhedron can acquire an effective inert gas configuration (8 valence electrons for a main group element and 18 for a transition metal atom). 

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