Phases preservation

If the sign of kj is equal to that of b, the reaction is phase preserving, if the signs are different, the reaction is phase inverting. 

By using the determinant fomi of the electronic wave functions, it is readily shown that a phase-inverting reaction is one in which an even number of election pairs are exchanged, while in a phase-preserving reaction, an odd number of electron pairs are exchanged. This holds for Htickel-type reactions, and is demonstrated in Appendix A. For a definition of Hilckel and Mbbius-type reactions, see Section III. 

There are two independent coordinates that define the plane of a loop. If the loop is phase inverting, one of these coordinates must be phase inverting, the other, phase preserving. Out of the infinite number of possible candidates, a convenient choice are reaction coordinates (Section I). Any one of the three reaction coordinates connecting two of the anchors can be used for the... 

Figure 4. The H3 and H4 loops. Ac the center, the conical intersections are shown schematically an equilateral triangle for H3 and a perfect tetrahedron for Kt, <2p> Jid Q, are the phase-preserving and phase-inverting coordinates, respectively.

Figure 5. A cut across the ground state (GS) and the excited state (ES) potential surfaces of the H4 system. The parameter Qp is the phase preserving nuclear coordinate connecting the H(lll) with the transition state between H(I) and H(1I) (Fig, 4). Keeping the phase of the electronic wave function constant, this coordinate leads from the ground to the excited state. At a certain point, the two surfaces must touch. At the crossing point, the wave function is degenerate.

Adopting the view that any theory of aromaticity is also a theory of pericyclic reactions [19], we are now in a position to discuss pericyclic reactions in terms of phase change. Two reaction types are distinguished those that preserve the phase of the total electi onic wave-function - these are phase preserving reactions (p-type), and those in which the phase is inverted - these are phase inverting reactions (i-type). The fomier have an aromatic transition state, and the latter an antiaromatic one. The results of [28] may be applied to these systems. In distinction with the cyclic polyenes, the two basis wave functions need not be equivalent. The wave function of the reactants R) and the products P), respectively, can be used. The electronic wave function of the transition state may be represented by a linear combination of the electronic wave functions of the reactant and the product. Of the two possible combinations, the in-phase one [Eq. (11)] is phase preserving (p-type), while the out-of-phase one [Eq. (12)], is i-type (phase inverting), compare Eqs. (6) and (7). Normalization constants are assumed in both equations ... 

Phase-preserving transition state (11) Phase-inverting transition state (12)... 

This is an example of a Mobius reaction system—a node along the reaction coordinate is introduced by the placement of a phase inverting orbital. As in the H - - H2 system, a single spin-pair exchange takes place. Thus, the reaction is phase preserving. Mobius reaction systems are quite common when p orbitals (or hybrid orbitals containing p orbitals) participate in the reaction, as further discussed in Section ni.B.2. 

Electi ocyclic reactions are examples of cases where ic-electiDn bonds transform to sigma ones [32,49,55]. A prototype is the cyclization of butadiene to cyclobutene (Fig. 8, lower panel). In this four electron system, phase inversion occurs if no new nodes are fomred along the reaction coordinate. Therefore, when the ring closure is disrotatory, the system is Hiickel type, and the reaction a phase-inverting one. If, however, the motion is conrotatory, a new node is formed along the reaction coordinate just as in the HCl + H system. The reaction is now Mdbius type, and phase preserving. This result, which is in line with the Woodward-Hoffmann rules and with Zimmerman s Mdbius-Huckel model [20], was obtained without consideration of nuclear symmetry. This conclusion was previously reached by Goddard [22,39]. 

We have seen (Section I) that there are two types of loops that are phase inverting upon completing a round hip an i one and an ip one. A schematic representation of these loops is shown in Figure 10. The other two options, p and i p loops do not contain a conical intersection. Let us assume that A is the reactant, B the desired product, and C the third anchor. In an ip loop, any one of the three reaction may be the phase-inverting one, including the B C one. Thus, the A B reaction may be phase preserving, and still B may be attainable by a photochemical reaction. This is in apparent contradiction with predictions based on the Woodward-Hoffmann rules (see Section Vni). The different options are summarized in Figure 11. 

Figure 11. Three typical loops for the case where A is the reactant and B—the desired product. Loops in which a conical intersection may be found are (a) and (c). A loop that does not encircle a conical intersecdon is (h). In loop (a) the A B reacdon is phase inverting, and in loops (b) and c) it is phase preserving.

Figure 23. A Loiigiiet-Higgms loop around the Jahn-Teller degeneracy of CPDR at D h symmetry, preserve and Qinv n aje the phase-inverting and phase-preserving coordinates that define the loop.

Figure 29, The effect of the phase-preserving component of the degenerate 2 distorting mode, It may be regarded as a major component of the reaction coordinate that leads to the A] structure (going left, one phase of the mode). Going right, the other phase of the same vibration, the B2 state is formed. (A type-V structure is also obtained along the same coordinate).

The transformation of ethylene to the carbene requires the re-pairing of three electron pairs. It is a phase-preserving reaction, so that the loop is an ip one. The sp -hybridized carbon atom formed upon H transfer is a chiral center consequently, there are two equivalent loops, and thus conical intersections, leading to two enantiomers. 

The p stands for phase-preserving reaction, Che i for phase inverting. 

The p stands for the phase-preserving reacdon, the i for the phase inverting. 

The reproducibility can be greatly affected by the conditions and the time of mobile phase preservation. 

Phase-preserving reactions, phase-change rule, pericyclic reactions, 449-450... 

C, the third anchor is obtained from the in-phase combination of A) and B), as shown in Section I. Therefore, there is always a phase-preserving coordinate connecting C and the vicinity of the TS between A and B. We shall make use of this property in the practical application of the method. 

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