Coalescence spectrum

Figure B2.4.3. Proton NMR spectrum of the aldehyde proton in N-labelled fonnainide. This proton has couplings of 1.76 Hz and 13.55 Hz to the two amino protons, and a couplmg of 15.0 Hz to the nucleus. The outer lines in die spectrum remain sharp, since they represent the sum of the couplings, which is unaffected by the exchange. The iimer lines of the multiplet broaden and coalesce, as in figure B2.4.1. The other peaks in the 303 K spectrum are due to the NH2 protons, whose chemical shifts are even more temperature dependent than that of the aldehyde proton.

The c/s-fused diaziridines (31a) and (31b) are also an equilibrium system, interchanging exo and endo positions of methyl and ethyl groups. The NMR spectrum shows two methyl peaks at 0 °C, coalescing to a single sharp peak at 75 °C. The ethyl group shows the sharp characteristic quartet-triplet splitting pattern at 75 °C (74JOC3187). 

This is most readily studied with cyclohexane- /n in which 11 of the 12 protons are replaced with deuterium. The spectrum of cyclohexane- /n resembles the behavior shown in Fig. 4-8 at about — 100°C (the slow exchange regime) two sharp lines are seen these broaden as the temperature is increased, reaching coalescence at — 61.4°C, and becoming a single sharp line at higher temperatures. (The deuterium nuclei must be decoupled by rf irradiation.) Rate constants t for the conversion were measured over the temperature range — 116.7°C to — 24.0°C by Anet and Bourne. It is probable that the chair-chair inversion takes place via a boat intermediate. 

When accelerated sufficiently, amplitude-frequency modulation in the absence of dephasing results in signal monochromatization, just like in the case of pure frequency modulation. Before the spectrum collapses, exchange between branches causes their broadening, but after collapse it provides their coalescence into a single line at frequency... 

Let us come back to the sample preparation A drop of solution containing silver nanoparticles dispersed in hexane is deposited on the substrate. The nanocrystals can be removed by washing the substrate and collected in hexane. The absorption spectrum of silver particles recorded before and after deposition remains the same. This indicates that coalescence does not take place. Similar behavior was observed by using HOPG as a substrate [6,35]. 

But don t assume that just because your compound exhibits restricted rotation, you must run it hot, to do it justice. Not so Sometimes, the barrier to rotation is just too high to allow simplification by heating. Remember - it is easier to deal with a spectrum of two, sharp rotamers than a broad semi-coalesced mess ... 

For pulses shorter than v lps the sepctrum will be broader and less pronounced that for pulses longer than 1 ps. Otherwise stated, the electron states immediately after excitation find themselves in a "foreign lattice" and this introduces strains which take finite time to diffuse before the ir-electrons accomodate themselves in a new lattice. These initial strains broaden the spectrum in the initial stage of excitation (up to 1 ps) for time longer than 1 ps the spectrum coalesces to the one observed with very long pul-esor stationnary sources. 

Reaction of 3 with Ph3C+PF6" resulted in the formation of methylidene complex [(n-C5H5)Re(N0)(PPh3)(CH2)]+ PF6 (8) in 88-100% spectroscopic yields, as shown in Figure 11. Although 8 decomposes in solution slowly at -10 °C and rapidly at 25 °C (She decomposition is second order in 8), it can be isolated as an off-white powder (pure by H NMR) when the reaction is worked up at -23 °C. The methylidene H and 13C NMR chemical shifts are similar to those observed previously for carbene complexes [28]. However, the multiplicity of the H NMR spectrum indicates the two methylidene protons to be non-equivalent (Figure 11). Since no coalescence is.observed below the decomposition point of 8, a lower limit of AG >15 kcal/mol can be set for the rotational barrier about the rhenium-methylidene bond. 

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