Single-Bond Twisting Mechanism

In the family of stilbazolium dyes DASPMI, DPS etc., a similar three-state mechanism is active leading in this case to single-bond twisted TICT species with a high intrinsic nonradiative rate [108,109] probably connected with the ionic nature of the dyes (charge shift, see Sect. 4.5). This results in similar lifetime maxima as a function of temperature as for DCS but sizeably shifted to lower temperatures with respect to DCS [96]. 

Two structurally unrelated immunosuppressant drugs, cyclosporin A and FK506, have been shown to bind to separate proteins, which have in common the ability to catalyse the interconversion (8) of the cis and trans rotamers of peptidyl-proline bonds of peptide substrates. A profound change in the conformation, and hence the shape and binding properties of the protein, may result. The mechanism of this isomerization appears, on the basis of recent work (Rosen et al., 1990 Van Duyne et al., 1993 Albers et al., 1990), to involve simple twisting about the amide bond, rather than such alternatives as conversion to a C-N single bond by addition of a nucleophile to C=0.y The proteins which catalyse the reaction may be... 

The E,Z-photoisomerization of previtamin D to tachysterol has also received recent attention. Jacobs and coworkers examined the process in various solvents at 92 K and found evidence for the formation of a triene intermediate which converts thermally (Ea ca 6.5 kcal mol 1) to the more stable tEc rotamer of tachysterol (tEc-T equation 58)230. The rate of this conversion is viscosity dependent. They identified this intermediate as the cEc rotamer, produced by selective excitation of the cZc rotamer of previtamin D. In a re-examination of the low temperature ,Z-photoisomerization of previtamin D as a function of excitation wavelength, Fuss and coworkers have suggested an alternative mechanism, in which tEc-1 is produced directly from cZc-P and cEc-T directly from tZc-P (equation 59)103. This mechanism involves isomerization about both the central double bond and one of its associated single bonds—the hula-twist mechanism of Liu and Browne101 — and involves a smaller volume change than the conventional mechanism for ,Z-isomerization. The vitamin D system has also been the subject of recent theoretical study by Bemardi, Robb and Olivucci and their co workers232. 

The photoisomerization of all-s-trans-all-trans 1,3,5,7-octatetraene at 4.3 K illustrates the need for a new mechanism to explain the observed behavior [150]. Upon irradiation, all-s-trans-all-trans 1,3,5,7-octatetraene at 4.3 K undergoes conformational change from all-s-trans to 2-s-cis. Based on NEER principle (NonEquilibrium of Excited state Rotamers), that holds good in solution, the above transformation is not expected. NEER postulate and one bond flip mechanism allow only trans to cis conversion rotations of single bonds are prevented as the bond order between the original C C bonds increases in the excited state. However, the above simple photochemical reaction is explainable based on a hula-twist process. The free volume available for the all-s-trans-all-trans 1,3,5,7-octatetraene in the //-octane matrix at 4.3 K is very small and under such conditions, the only volume conserving process that this molecule can undergo is hula-twist at carbon-2. 

In order to examine possible conformational differences between the different classes of poly(RCOT)s, both force-field (MM2) [132] and semiempirical quantum mechanical (AMI) [133] calculations on model polyene oligomers were employed (Fig. 10-23) [34]. Using either routine, it is observed that the single bonds adjacent to the trisubstituted double bond (0] and 2) both strongly deviate from planarity in the models of the soluble polymers. In contrast, in the model of trans- poly (terr-butoxyCOT), an insoluble polymer, j is large, but 2 is not. The good correlation between polymer solubility and calculated chain twist is indicated... 

Figure 10-24 Twist angles about the single bonds adjacent to the substituted bond of a poly(RCOT) oligomer, modeled using molecultu mechanics [34], Those polymers with twist angles greater than the position of the dashed line are soluble in the trans form.

A volume-conserving mechanism such as hula-twist (H-T) that requires a concomitant twisting of the double bond and the adjacent single bond to accomphsh the double-bond ds-trans isomerization, different from the usual one-bond rotation mechanism. 

For ds-trans isomerization in highly condensed media at very low temperature <77 K, liu and Hammond postulated mechanisms called one-bond flip and hula-twist mecdianism [35-38]. According to the H-T mechanism, isomerization takes place not by the one-bond rotation around the double bond but by the concomitant twist of the double bond and the adjacent single bond to accomplish the double-bond isomerization (Figure 4.10). These mechanisms were assumed to reduce free volume... 

If the assignments in Scheme 7 are correct, formation of the Tachy products involves rotations at adjacent double and single bonds, providing the first experimental verification of an outcome consistent with Liu s hula-twist mechanism for ds— trans photoisomerization. They have stimulated the recent resurrection of this mechanism with spedal attention to the key role of the volume-conserving requirements of the rigid medium. ... 

Detailed mechanisms of intramolecular rearrangement reactions have been difficult to determine. Classical rate measurements seldom lead to unambiguous mechanistic predictions. Generally only after extensive examination of concentration, solvent, and substituent effects on the reaction rate can a general mechanistic class be proposed for example, intra vs intermolecular or bond rupture of a bidentate chelate vs non-bond rupture twist pathways. Indeed, only two examples of slow complexes are known where detailed rate comparisons for geometrical and optical iso-merizations were made and used to eliminate several mechanisms however, a single most probable pathway was not demonstrated in either case.12,13 Only with DNMR can detailed environmental site interchanges be directly observed and with this in-... 

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