Functional derivatives spectroscopic analysis

The actual calculation consists of minimizing the intramolecular potential energy, or steric energy, as a function of the nuclear coordinates. The potential-energy expressions derive from the force-field concept that features in vibrational spectroscopic analysis according to the G-F-matrix formalism [111]. The G-matrix contains as elements atomic masses suitably reduced to match the internal displacement coordinates (matrix D) in defining the vibrational kinetic energy T of a molecule ... 

The second part of the chapter deals with several kinds of asymmetric reactions catalyzed by unique heterobimetallic complexes. These reagents are lanthanoid-alkali metal hybrids which form BINOL derivative complexes (LnMB, where Ln = lanthanoid, M = alkali metal, and B = BINOL derivative). These complexes efficiently promote asymmetric aldol-type reactions as well as asymmetric hydrophosphonylations of aldehydes (catalyzed by LnLB, where L = lithium), asymmetric Michael reactions (catalyzed by LnSB, where S = sodium), and asymmetric hydrophosphonylations of imines (catalyzed by LnPB, where P = potassium) to give the corresponding desired products in up to 98% ee. Spectroscopic analysis and computer simulations of these asymmetric reactions have revealed the synergistic cooperation of the two different metals in the complexes. These complexes are believed to function as both Brpnsted bases and as Lewis acids may prove to be applicable to a variety of new asymmetric catalytic reactions.1,2... 

In addition to functionalization of polyanilines with sulfonic and carboxylic acids, the corresponding phosphonic acid derivatives have been prepared, o-Aminobenzylphosphonic acid was prepared as shown in Figure 20.54 [42,43]. Oxidative coupling of the above monomer in an acidic medium yielded poly(o-aminobenzylphosphonic acid) (Figure 20.55). Spectroscopic analysis was consistent with head-to-tail oxidative coupling through the /Jara-position. The as-prepared polymer was in its emeraldine oxidation state in which 43% of the N-atoms were protonated by the pendent acid. This polymer was insoluble in both non-aqueous solvents and aqueous acidic solutions. 

The presumed supramolecular oligomers were subjected to concentration-dependent absorption spectroscopic analysis in solution. Fits of the extinction coefficients obtained as a function of concentration to an isodesmic model allowed association constants to be derived (cf. Table 12.1). On this basis, it was noted that... 

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