• DOI:10.1021/JA9621152
• Corpus ID: 55464208

Geometry of the Phosphate Group and Its Interactions with Metal Cations in Crystals and ab Initio Calculations

@article{Schneider1996GeometryOT,
  title={Geometry of the Phosphate Group and Its Interactions with Metal Cations in Crystals and ab Initio Calculations},
  author={Bohdan Schneider and A. Kabelac and Pavel Hobza},
  journal={Journal of the American Chemical Society},
  year={1996},
  volume={118},
  pages={12207-12217}
}

• B. Schneider, A. Kabelac, P. Hobza
• Published 4 December 1996
• Chemistry
• Journal of the American Chemical Society

The phosphate geometry was studied in crystal environment by analyzing 178 crystal structures and in vacuo by ab initio calculations of (di)hydrogen and dimethyl phosphates and a diphosphate model system, CH3OP(O2)O(CH2)3OP(O2)OCH3 (diPh), at the MP2 and HF levels. Since charge determines the phosphate stereochemistry, uncharged, −1, and −2 phosphates were analyzed separately. The PO and OPO bonding parameters depend only on charge and the number of carbon substituents while the remaining parameters depend also on substituent type; the largest sensitivity was observed for the CO and COP parameters. An acceptable agreement between the crystal and ab initio geometries was obtained only when basis sets contained polarization functions and a model system included a counterion (Na+). In uncharged and −1 phosphates, the COPO(C) torsion angles prefer the ±sc regions. These phosphates substituted by cyclic Csp3, noncyclic Csp3, or Car carbons have characteristic torsion distributions. Conclusion from both analysi...