Near-synchronous mechanism

It is apparent there is a definite advantage to operating under solvent-free conditions. The specific microwave effect is here of low magnitude, but evident, because after 3 min the yield increases from 64 to 98%. Prolongation of the reaction time with classical heating led to an equivalent result. The microwave effect is rather limited here, because of a near-synchronous mechanism. 

The aqua ion Au(H20)4+ has not been characterized either in solution or in the solid state. Most of the substitution studies have involved the halide complexes AuXj and Au(NH3) (Ref. 319). A number of earUer generalizations have been confirmed. Rates are very sensitive to the nature of both entering and leaving ligands and bond formation and breaking are nearly synchronous. The double-humped energy profiles witnessed with Pd(II) and Pt(II) are not invoked the five-coordinate species resulting from an associative mechanism is the transition state ... 

In contrast to strongly solvent-dependent [2- -2]cycloaddition reactions, which proceed through a 1,4-dipolar zwitterionic intermediate by a two-step mechanism or through a dipolar activated complex by a one-step mechanism cf. Section 5.3.2, and Eqs. (5-33) to (5-35) [92, 94-107], [2- -2]cycloadditions are also known that exhibit concerted, nearly synchronous bond formation without significant charge separation on activation in the transition state. An example is given in Eq. (5-47). Since the rate constant for this diphenylketene/styrene addition is practically independent of solvent polarity [140], it can be classed as concerted. 

The mechanism of the carbo-Diels-Alder reaction has been a subject of controversy with respect to synchronicity or asynchronicity. With acrolein as the dieno-phile complexed to a Lewis acid, one would not expect a synchronous reaction. The C1-C6 and C4—C5 bond lengths in the NC-transition-state structure for the BF3-catalyzed reaction of acrolein with butadiene are calculated to be 2.96 A and 1.932 A, respectively [6]. The asynchronicity of the BF3-catalyzed carbo-Diels-Alder reaction is also apparent from the pyramidalization of the reacting centers C4 and C5 of NC (the short C-C bond) is pyramidalized by 11°, while Cl and C6 (the long C-C bond) are nearly planar. The lowest energy transition-state structure (NC) has the most pronounced asynchronicity, while the highest energy transition-state structure (XT) is more synchronous. 

The difference between the various pulse voltammetric techniques is the excitation waveform and the current sampling regime. With both normal-pulse and differential-pulse voltammetry, one potential pulse is applied for each drop of mercury when the DME is used. (Both techniques can also be used at solid electrodes.) By controlling the drop time (with a mechanical knocker), the pulse is synchronized with the maximum growth of the mercury drop. At this point, near the end of the drop lifetime, the faradaic current reaches its maximum value, while the contribution of the charging current is minimal (based on the time dependence of the components). 

Simultaneous with the publication of Hocker et al., there appeared the results of Yardley and Moore [142] on laser-excited vibrational fluorescence in CH4. A mechanically chopped He-Ne 3.39-micron laser [143, 144] was used to excite the asymmetric stretching [/ = 2948 cm-1 (36.55 X 10-2 eV)] vibration, i>3 (see Figure 3.17). The optical arrangement is shown in Figure 3.18. The He-Ne laser tube, 220 cm in length, is shown on the left. Mx, M2, and Ms are mirrors Bx and B2 are baffles to eliminate stray light Lx and L2 are lenses which focus the laser output into a collimated beam having a diameter of 2 mm, and thence, into a Pyrex fluorescence cell. At the focal point between Li and L2 is a chopper wheel, to produce a nearly perfect square wave modulated at frequencies between 600 and 10,000 Hz. An audio oscillator and a 60-W amplifier are used to drive the synchronous chopper motor. An InSb infrared detector (response time of about 4 nsec) is used to... 

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