TY - JOUR

T1 - Positively charged phosphorus as a hydrogen bond acceptor

AU - Hansen, Anne Schou

AU - Du, Lin

AU - Kjærgaard, Henrik Grum

PY - 2014

Y1 - 2014

N2 - Phosphorus (P) is an element that is essential to the life of all organisms, and the atmospheric detection of phosphine suggests the existence of a volatile biogeochemical P cycle. Here, we investigate the ability of P to participate in the formation of OH···P hydrogen bonds. Three bimolecular alcohol-trimethylphosphine complexes have been detected. Initially, the complexes were detected using matrix isolation spectroscopy, which favors complex formation. Subsequently, the fundamental OH-stretching vibration was observed in room-temperature gas-phase spectra. On the basis of our measured OH-stretching frequency red shifts and quantum chemical calculations, we find that P is an acceptor atom similar in strength to O and S and that all three P, O, and S atoms are weaker acceptors than N. The quantum chemical calculations show that both H and P in the OH···P hydrogen bond have partial positive charges, as expected from their electronegativities. However, the electrostatic potentials show a negative potential area on the electron density surface around P that facilitates formation of hydrogen bonds.

AB - Phosphorus (P) is an element that is essential to the life of all organisms, and the atmospheric detection of phosphine suggests the existence of a volatile biogeochemical P cycle. Here, we investigate the ability of P to participate in the formation of OH···P hydrogen bonds. Three bimolecular alcohol-trimethylphosphine complexes have been detected. Initially, the complexes were detected using matrix isolation spectroscopy, which favors complex formation. Subsequently, the fundamental OH-stretching vibration was observed in room-temperature gas-phase spectra. On the basis of our measured OH-stretching frequency red shifts and quantum chemical calculations, we find that P is an acceptor atom similar in strength to O and S and that all three P, O, and S atoms are weaker acceptors than N. The quantum chemical calculations show that both H and P in the OH···P hydrogen bond have partial positive charges, as expected from their electronegativities. However, the electrostatic potentials show a negative potential area on the electron density surface around P that facilitates formation of hydrogen bonds.

KW - alcohols

KW - hydrogen bonding

KW - molecular complexes

KW - phosphorus

U2 - 10.1021/jz502150d

DO - 10.1021/jz502150d

M3 - Journal article

C2 - 26278958

AN - SCOPUS:84915785012

VL - 5

SP - 4225

EP - 4231

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 23

ER -