Intramolecular hydrogen bond complex

J. Howard, J. Tomkinson, J. Eckert, J.A. Goldstone A.D. Taylor (1983). J. Chem. Phys., 78, 3150-3155. Inelastic neutron scattering studies of some intramolecular hydrogen bonded complexes a new correlation of gamma-(OHO) vs R(00). 

Dielectric measurements were used to evaluate the degrees of inter- and intramolecular hydrogen bonding in novolac resins.39 The frequency dependence of complex permittivity (s ) within a relaxation region can be described with a Havriliak and Negami function (HN function) ... 

Coco, S., Cordovdla, C., EspineL P. and Marti n-Alvarez, J. (2006) Structural switching in luminescent polynudear gold imidoyl complexes by intramolecular hydrogen bonding. Organometallics, 25, 2700-2703. 

This work raises some interesting issues. The first is that the stoichiometry of a complex is not necessarily the most obvious. For example, it was reported initially that phthalic acid formed a 2 1 complex with alkoxystil-bazole [34], when in fact a careful study carried out by constructing a binary phase diagram (Fig. 11) revealed the complex to have a 1 1 ratio of the two components [35]. The reluctance of the system to form the more obvious 2 1 complex may relate to the presence of intramolecular hydrogen bonding or could even relate to the change in the pfCa of the second acid proton on com-plexation. 

The aromatic spacer group of the model receptors prevent the formation of intramolecular hydrogen bonds between the opposing carboxyls yet these functions are ideally positioned for intermolecular hydrogen bonds of the sort indicated in 32. The acridine derivatives do indeed form stoichiometric complexes with oxalic, malonic (and C-substituted malonic acids) as well as maleic and phthalic acids, Fumaric, succinic or glutaric acids did not form such complexes. Though protonation appears to be a necessary element in the recognition of these diacids, the receptor has more to... 

The optically active Schiff bases containing intramolecular hydrogen bonds are of major interest because of their use as ligands for complexes employed as catalysts in enantioselective reactions or model compounds in studies of enzymatic reactions. In the studies of intramolecularly hydrogen bonded Schiff bases, the NMR spectroscopy is widely used and allows detection of the presence of proton transfer equilibrium and determination of the mole fraction of tautomers [21]. Literature gives a few names of tautomers in equilibrium. The OH-tautomer has been also known as OH-, enol- or imine-form, while NH tautomer as NH-, keto-, enamine-, or proton-transferred form. More detail information concerning the application of NMR spectroscopy for investigation of proton transfer equilibrium in Schiff bases is presented in reviews.42-44... 

The transfer of a proton between an acidic and a basic group within the same molecule is often more complex than the process shown in (1). The proton may be transferred along hydrogen-bonded solvent molecules between the acidic and basic groups if these are too remote to permit formation of an intramolecular hydrogen bond. Alternatively, two inter-molecular proton transfers with an external acid or base may be necessary. Tautomerisation of oxygen and nitrogen acids and bases (3) will be described in Section 6. The reactions are usually quite rapid and fast reaction... 

Fig. 6. Schematic diagram of the peptide-protein interaction mode as seen in the crystallo-graphically refined structured of the Lck SH2 domain-peptide complex, Protein Databank entry code 1 LKK.PDB. The residues directly engaged in intramolecular hydrogen bonds (dotted lines) are labeled explicitly... 

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