D-H... M hydrogen bonds

The strength of hydrogen bonds and their ability to contribute to reliable supra-molecular synthons are not the only criteria for judging the importance of different types of hydrogen bonds. Unless such hydrogen bonds are readily accessible, they will inevitably be of limited use, although perhaps of use in specialized cases. This will inevitably be the case with M-H A and D-H M hydrogen bonds, which are only accessible for certain classes of metal complex. At the other... 

Palin, D. E., Powell, H. M., Hydrogen bond linking of quinol molecules. Nature 1945, 156, 334-335. 

Table 2 Some dihydrogen bond strengths (kcal mol ), deduced from Av(NH) and Av OH) IR spectroscopic data, for intermolecular adducts of some d and d complexes with typical proton donors, indicating that direct X-H -M hydrogen bonding is not predominant data taken from ref 12b...

Abraham, M. H., Ibrahim, A., Zissimos, A. M., Zhao, Y. H., Comer, J. E., Reynolds, D. Application of hydrogen bonding calculations in property based dmg design. Drug Discov. Today 2002, 7, 1056-1063. 

D-a-hydroxyvaleric add, L-valine, L-lactic acid] 3, having a 36-atom ring with twelve carbonyl oxygen atoms. From i.r. (65) and n.m.r. (66) spectroscopy it was established that the cationic complex has three-fold symmetry with the peptide carbonyl oxygen atoms involved in N—H... O hydrogen bonding. According to optical rotatory dispersion (ORD) and... 

Wurpel, G. W. H., Brouwer, A. M., van Stokkum, I. H. M., Farran, A., Leigh, D. A., Enhanced hydrogen bonding induced by optical excitation Unexpected subnanosecond photoinduced dynamics in a peptide-based [2]rotaxane. J. Am. Chem. Soc. 2001, 123, 11327-11328. 

Section C Thomas, P.J., Qu, B.H. and Pederson, P.L. (1995) Defective protein folding as a basis of human disease. Trends Biochem. Sci. 20, 456-459. Wahl, M.C. and Sundaralingam, M. (1997) C-H...O hydrogen bonding in biology. Trends Biochem. Sci. 22, 97-102. Hampton, R., Dimster-Denk, D. and Rine, J. (1996) The biology of HMG-CoA reductase the pros of contra-regulation. Trends Biochem. Sci. 21, 140-145. Kantrowitz, E.R. and Lipscomb, W.N. (1990) Escherichia coli aspartate trans-carbamoylase the molecular basis for a concerted allosteric transition. Trends Biochem. Sci. 15, 53-59. 

Clearly specific to inorganic systems are hydrogen bonds that directly involve metal atoms, M-H A and D-H M, i.e. those in the Metal Domain. A survey of crystal structures has illustrated that M-H O hydrogen bonds appear to resemble C-H O hydrogen bonds, although the former are of course far less abundant. The extent to which such hydrogen bonds may be useful in crystal engineering is addressed in Section 6. 

Figure 25 Structure of [Co(terpy-NH)2](PF6)2 showing assembly of cationic cobalt complexes by self-complimentary N-H N hydrogen bonds (top, middle) to give a 2D grid (bottom). Reproduced from V. Ziener, E. Brevning, J.-M. Lehn, E. Wegelius, K. Rissanen, G. Baum, D. Fenske and G. Vaughn, Chem. Eur../., 6,4132-9 (2000) with permission of Wiley-VCH.

In an important paper, Braga, Grepioni, Desiraju and co-workers highlighted the abundance of C-H OC(M) hydrogen bonds in crystals of organometallic compounds [28b], The use of the CSD to analyse such hydrogen bonds across the series of d-block metals Ti-Ni led to a number of specific findings ... 

REF25 Hartmann, M., Wetmore, S. D. and Radom, L. (2001) C-H- - -X hydrogen bonds of acetylene, ethylene, and ethane with first- and second-row hydrides, J. Phys. Chem. A, 105, 4470 479... 

Hussein, M.A. and Millen, D.J. (1976) Hydrogen bonding in the gas phase. Part 4. Infrared spectroscopic investigation of O-H- - -O and C-H- - -N complexes alcohol + ether and trichloromethane + amine systems, J. Chem. Soc., Faraday Trans. 2 72, 693-699. 

Cheung, E.Y., McCabe, E.E., Harris, K.D.M., Johnston, R.L., Tedesco, E., Raja, K.M.P., and Balaram, P. (2002) C-H- - -O hydrogen bond mediated chain reversal in a peptide containing a 7-amino acid residue, determined directly from powder X-ray diffraction data, Angew. Chem., Int. Ed. Engl. 41, 494-496. 

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