Anti-bonding

The origin of a torsional barrier can be studied best in simple cases like ethane. Here, rotation about the central carbon-carbon bond results in three staggered and three eclipsed stationary points on the potential energy surface, at least when symmetry considerations are not taken into account. Quantum mechanically, the barrier of rotation is explained by anti-bonding interactions between the hydrogens attached to different carbon atoms. These interactions are small when the conformation of ethane is staggered, and reach a maximum value when the molecule approaches an eclipsed geometry. 

Anti-bonding tt orbital, 293 Atomic orbital resonance, 295 16/3-Azido- 17a-iodoandrostanes, 24 16p-Azido-17a-iodo-5a-androstan-3 -ol acetate, 28... 

The LUMO is similar to the HOMO, but the lobes do not align. Thi> appears more like an anti-bonding orbital. 

The same conclusion may again be reached by considering only the HOMO orbital. Figure 15.24. For the conrotatory path the orbital interaction leads directly to a bonding orbital, while the orbital phases for the disrotatory motion lead to an anti-bonding orbital. 

One-electron oxidation to [Rh2(OCOMe)4(H20)2]+ leads to an ion (violet to orange, depending on solvent) with a shorter Rh-Rh bond (2.317 A) than that in the neutral molecule (2.385 A), suggesting the electron has been removed from an orbital with anti-bonding character. 

In the MO scheme the rhodium atoms use their dxz y2 orbitals to form the Rh—O bonds, the remaining 4d orbitals are used to form four pairs of bonding and anti-bonding MOs (a, 8 and 7r) (Figure 2.37a). 

There is (a) cr-donation from a filled oxygen orbital to an empty platinum orbital and (b) 7r back-bonding from a filled metal d orbital into an empty oxygen 7r -anti-bonding orbital. 

Back-bonding, with formation of a 7r-bond, from a filled metal d orbital to an anti-bonding it -ethene orbital. 

Kasai and McLeod (57, 58) also studied a series of bimetallic diatomics, AgM (M = Mg, Ca, Sr, Be, Zn, Cd, or Hg), by ESR spectroscopy. For all of these species, the hyperfine coupling to the Ag nucleus was found to be isotropic. It was shown that the unpaired electron resides in an orbital resulting essentially from an anti-bonding combination of the valence s orbitals of the Ag and M atoms. A typical spectrum is shown in Fig. 13. 

Jorgensen CK (1975) Partly Filled Shells Constituting Anti-bonding Orbitals with Higher Ionization Energy than Their Bonding Counterparts. 22 49-81 Jorgensen CK (1975) Photo-Electron Spectra of Non-Metallic Solids and Consequences for Quantum Chemistry. 24 1-58... 

The repulsion of the thallium and oxygen lone pairs lead to a distortion of the Tl-6s lone pair, which is no longer totally spherical as one would intuitively expect for an s orbital. The thallium contributions involved in the anti-bonding combination are indeed of 97.7% s-, 1.8% p- and 0.5% d-character. Thus, a much less than expected p-character is found for the thallium orbital, which shows that extensive s-p mixing or hybridization is not essential for the lone pair to become stereochemically active. 

In summary, one can state that s-p-hybridization on the heavier main group metals is not responsible for the stereochemical activity of a lone pair. Instead, the general conclusion can be drawn that anti-bonding metal ns-ligand np interactions lead to structural distortions in order to minimize these unfavorable interactions. 

In contrast to chloride compounds, niobium oxides have a VEC of 14 electrons, due to an overall anti-bonding character of the a2u state, caused by a stronger Nb-O anti-bonding contribution. In some cases, the VEC cannot be determined unambiguously due to the uncertainty in the electron distribution between the clusters and additional niobium atoms present in the majority of the structures. The 14-electron compounds exhibit semiconducting properties and weak temperature-independent paramagnetism. Unlike niobium chlorides, the oxides do not exhibit a correlation between the electronic configuration and intra-cluster bond distances. 

The number of valence electrons in niobium oxychloride clusters decreases as the number of oxide hgands increases (Table 6.4). The compound Cs2LuNbi Cli70 has the VEC of 16 as found in most chloride clusters, suggesting that the presence of one oxide ligand per cluster does not tip the balance between the Nb-Nb bonding and Nb-L anti-bonding contributions to the a2u state. The VEC of most clusters... 

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