C2v-symmetry

Static properties of some molecules ([193,277-280]). More recently, pairs of ci s have been studied [281,282] in greater detail. These studies arose originally in connection with a ci between the l A and 2 A states found earlier in computed potential energy surfaces for C2H in symmetry [278]. Similar ci s appear between the potential surfaces of the two lowest excited states A2 and B2 iit H2S or of 82 and A in Al—H2 within C2v symmetry [283]. A further, closely spaced pair of ci s has also been found between the 3 A and 4 A states of the molecule C2H. Here the separation between the twins varies with the assumed C—C separation, and they can be brought into coincidence at some separation [282]. 

To further illustrate these points dealing with orbital symmetry, consider the insertion of CO into H2 along a path which preserves C2v symmetry. As the insertion occurs, the degenerate n bonding orbitals of CO become hi and 62 orbitals. The antibonding n orbitals of CO also become hi and 62. The <5g bonding orbital of H2 becomes ai, and the antibonding H2 orbital becomes 62. The orbitals of the reactant... 

H2CO are energy-ordered and labeled aeeording to C2v symmetry in the Figure shown below as are the orbitals of the produet H2 + CO. 

An example will help illustrate these ideas. Consider the formaldehyde molecule H2CO in C2v symmetry. The configuration which dominates the ground-state waveflinction has doubly occupied O and C 1 s orbitals, two CH bonds, a CO a bond, a CO n bond, and two 0-centered lone pairs this configuration is described in terms of symmetry adapted orbitals as follows (Iai22ai23ai2lb2 ... 

All these compounds have (distorted) tetrahedral molecules, those of formula O2SX2 having C2v symmetry and the others Cj. Dimensions are in Table 15.15 the remarkably short O-S and S-F distances in O2SF2 should be noted (cf. above). Indeed, the implied strength of bonding in this molecule is reflected by the fact that it can be made by reacting the normally extremely inert compound SFg (p. 687) with the fluoro-acceptor SO3 ... 

The dithionite ion has a remarkable eclipsed stmcture of approximate C2v symmetry (Fig. 15.32b). The extraordinarily long S-S distance (239 pm) and the almost parallel SO2 planes (dihedral angle 30°) are other unusual features. Electron-spin-resonance studies have shown the presence of the S02 radical ion in solution ( 300ppm), suggesting the establishment of a monomer-dimer equilibrium 8204 ... 

Br20 a dark-brown solid moderately stable at —60° (mp —17.5° with decomposition), prepared by reaction of Bt2 vapour on HgO (cf. CI2O p. 846) or better, by low-temperature vacuum decomposition of BrOa. The molecule has C2v symmetry in both the solid and vapour phase with Br-O 185 1pm and angle BrOBr 112 2° as determined by EXAFS (extended X-ray absorption fine structure). It oxidizes I2 to I2O5, benzene to 1,4-quinone, and yields OBr in alkaline solution. 

The whole sequence of reactions represents a tour de force in the elegant manipulation of extremely reactive compounds. F3CIO2 is a violent oxidizing reagent but forms stable adducts by fluoride ion transfer to Lewis acids such as BF3, AsF5 and PtFe. The structures of F3CIO2 and [F2C102] have C2v symmetry as expected (Fig. 17.26e and i). 

A solution to the problem is to define an axis of symmetry through the use of dummy atoms. To take the case of fiiran, the Z-matrix of Figure 10.7 will retain C2v symmetry. 

Figure 15.11 Reaction of two ethylenes to form cyclobutane under C2v symmetry...

In addition, a chlorine ion most probably replaces the fluoride ion located on the rotation diad axis of the heptacoordinated complex with C2v symmetry otherwise splitting of the band would be observed. Replacement of the ligand in any other position would reduce the symmetry from C2v to Cj. 

Distinguishing between the fac- and mer-isomers is theoretically possible with far-IR spectra, as the mer-isomer (C2v symmetry in the coordination sphere) should give rise to three u(Os—X) stretching bands, while the C3v... 

We will conclude this section on theory with such a case. In Section 8.3 it was shown that the influence of substituents on the rate of dediazoniation of arenediazonium ions can be treated by dual substituent parameter (DSP) methods, and that kinetic evidence is consistent with a side-on addition of N2. We will now discuss these experimental conclusion with the help of schematic orbital correlation diagrams for the diazonium ion, the aryl cation, and the side-on ion-molecule pair (Fig. 8-5, from Zollinger, 1990). We use the same orbital classification as Vincent and Radom (1978) (C2v symmetry). 

Transannular interaction via the electron-delocalization mechanism was found, but lessened by 10-15% for the ligand superhyperfine splitting and 30-35% for the hyperfine splitting (62) in the epr spectrum. The crystal structure of [VOS2CNEt2)2] shows that the molecular core has the expected C2V symmetry [V-0 = 159.1(4), V-S = 138.7(2)-241.0(2) pm] (63). Magnetic and spectral data provided evidence for a tetragonal, pyramidal structure (VII) for these complexes. Like many other coordinatively unsaturated, metal... 

As expected, the hexagonal chair form of Se with 03a symmetry, occurring in the solid hexasulfur, is the most stable form of hexasulfur, due to its minimal strain. The boat conformer of C2V symmetry is 50 kj mol less stable than the chair form [54]. The Dsa—>C2v interconversion requires to overcome a barrier of ca. 125 kJ mol A structure of C2 symmetry, which is a local minimum at the HF/3-21G level [49, 50], is not a stationary point at higher levels of theory [54, 55]. 

The large energy differences between the global minimum structure of C2v symmetry and the other isomers indicate that equilibrium sulfur vapor will contain only minute amounts of the latter, even at very high temperatures. However, under non-equilibrium conditions as in electrical discharges or by illumination with a laser as in Raman spectroscopy unstable isomers may be formed and detected. 

The molecular structures of the isolated polysulfide monoanions 8 with n=2-9 have been studied by density functional calculations and those of the smaller ions also by ab initio MO calculations. Compared to the neutral 8 molecules the extra electron occupies an antibonding orbital resulting in longer 88 bonds. The species 83 is bent and of C2V symmetry (a=115°) [140, 141]. 84 was calculated to be a planar ion of C2V symmetry (similar to the neutral molecule 84) but the planar C2h structure is only slightly less stable [140, 141]. The most stable isomer of 85 is a chain of Q symmetry sim-... 

Symmetry class S2O2 (C2v) Symmetry class S2O2 (C2h)... 

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