Coalescence, NMR

There continue to be reports on rotations of coordinated alkenes, alkynes, etc. about the metal-ligand axis rapid enough to coalesce nmr signals. In square planar complexes the alkene is preferentially orientated perpendicularly. Orientations for other coordination geometries have also been examined experi-... 

Figure B2.4.1. Proton NMR spectra of the -dimethyl groups in 3-dimethylamino-7-methyl-l,2,4-benzotriazine, as a fiinction of temperature. Because of partial double-bond character, there is restricted rotation about the bond between the dunethylammo group and the ring. As the temperature is raised, the rate of rotation around the bond increases and the NMR signals of the two methyl groups broaden and coalesce.

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.

Although the thermodynamic aspects of acylotropy are well documented, there have been few kinetic studies of the process. The activation barrier is much higher than for prototropy and only Castells et al. (72CC709) have succeeded in observing a coalescence phenomenon in H NMR spectra. At 215 °C in 1-chloronaphthalene the methyl groups of N-phenyl-3,5-dimethylpyrazole-l-carboxamide coalesce. The mechanism of dissociation-combination explains the reversible evolution of the spectra (Scheme 9). 

Nl pyrazoles NMR Coalescence temperature (°C) Activation energy (kJmoP ) Ref. 

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). 

Below 100 °C tri-t-butyldiaziridinimine (176) only undergoes inversion at the exocyclic nitrogen, as evidenced by coalescence of NMR signals at about 50 °C. Heating for 1 h to 150 °C, however, results in clean formation of ( )-azoisobutane and t-butyl isocyanide. 

Figure 4-8. NMR absorption by a hypothetical two-identical site system with chemical exchange (/I) Slow exchange limit. (B) Moderately slow exchange. (D) Coalescence. (F) Fast exchange limit.

The only other C5(i-Pr)5 complex, Mo(Pr5Cp)(CO)3CH3 (30) also shows fluxional iso-propyl groups at 100 °C, but below the coalescence temperature two isomers in the ratio 4 3 are obeserved according to, 3C NMR spectra. They are... 

A Relaxation time measurement in the solid (Al) in solution (A2). B Mechanical spectroscopy. C Variable-temperature NMR spectroscopy (coalescence temperature measurement). D Variable-temperature EPR spectroscopy... 

Although 1- and/or 4-acylated hydroquinoxalines might not be considered as regular quinoxalone ketones, they are included here for pragmatic reasons. Examination of the NMR chemical shifts for H5 and H8 in l,4-diacyl-l,2,3,4-tetrahydroquinoxalines (197, R = Me, Et, Ph, etc.) indicated that the endo-exo conformation (shown) predominated in most such compounds at ambient temperatures. " However, this was disturbed in l,4-dibenzoyl-6,7-dimethyl-l,2,3,4-tetra-hydroquinoxaline (198), which showed a predominance of the exo-exo conformation (shown) below the coalescence temperature. ... 

Studies of flow-induced coalescence are possible with the methods described here. Effects of flow conditions and emulsion properties, such as shear rate, initial droplet size, viscosity and type of surfactant can be investigated in detail. Recently developed, fast (3-10 s) [82, 83] PFG NMR methods of measuring droplet size distributions have provided nearly real-time droplet distribution curves during evolving flows such as emulsification [83], Studies of other destabilization mechanisms in emulsions such as creaming and flocculation can also be performed. 

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