Hydrogen Bonds To Phosphorus Observed | Chemical & Engineering News
Volume 92 Issue 50 | p. 24 | Concentrates
Issue Date: December 15, 2014

Hydrogen Bonds To Phosphorus Observed

Department: Science & Technology
News Channels: Analytical SCENE
Keywords: H-bond, hydrogen-bond, phosphorus
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H (white) in methanol and P (orange) in trimethylphosphine both bear partial positive charges but form an H-bond, as seen in this model. Gray = carbon and red = oxygen.
Credit: J. Phys. Chem. Lett.
Illustration of P-bonding.
 
H (white) in methanol and P (orange) in trimethylphosphine both bear partial positive charges but form an H-bond, as seen in this model. Gray = carbon and red = oxygen.
Credit: J. Phys. Chem. Lett.

Researchers have found unusual hydrogen bonds to phosphorus in three bimolecular alcohol-trimethylphosphine complexes and have measured their strengths. H-bonds do not usually form to P. In the new study, in which a hydroxyl H atom bonds with P in another compound, P bears a partial positive charge, making H-bond formation especially unlikely. The work was carried out by Henrik G. Kjaergaard and coworkers at the University of Copenhagen (J. Phys. Chem. Lett. 2014, DOI: 10.1021/jz502150d). P. G. Sennikov of the Russian Academy of Sciences, in Nizhny Novgorod, and coworkers earlier observed H bonding to P in phosphine. Kjaergaard and coworkers believe that case to be the only other experimental observations of the phenomenon. In their study, although trimethylphosphine’s P atom has partial positive charge, its electrostatic potential surface also has a negative-potential area around the lone pair, and the H-bonds form at that spot. “This work clearly shows that we cannot continue to think of charge distribution as spherical in atoms, molecules, or even ions,” Kjaergaard says.

 
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