Calculated heats of formation of simple phosphinidenes (phosphanylidenes, R-P)

D. Szieberth, T. Veszpremi, M. T. Nguyen

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Ab initio MO and DFT calculations up to the coupled-cluster theory level, CCSD(T) with large 6-311++G(3df,2p) and cc-pVTZ basis sets, have been applied to determine the heats of formation of a series of simple phosphinidenes (R-P) that exhibit a triplet ground state. Three different exchange and isogyric reactions of the type RP + HX → HP + RX have been used as working reactions. A set of consistent values for ΔHf.298° (R-P) are evaluated as follows (values in kcal/mol): H3CP, 47.6; H2NP, 48.6; HOP, -0.5; FP, -12.5 (exp: -12.4); H3SiP, 61.9; H2PP, 58.0; HSP, 47.9; ClP, 30.0 (exp: 30.8); BrP, 40.0 (exp: 38.9) with an estimated error bar of ±2 kcal/mol. DFT/B3LYP calculations have been found to reproduce these values with acceptable accuracy. Empirical corrections for the DFT/B3LYP calculations were estimated and heats of formation for a series of other phosphinidenes were also evaluated using this correction: H2FCP, 10.2; HF2CP, -43.6; F3CP, -96.0; H2ClCP, 46.6; H2BrCP, 56.8; O=CHP, 34.6; S=CHP, 81.2; HN=CHP, 77.3; CH3CH2P, 45.4; H2C=CHP, 70.4; HC ≡ C-P, 100.5. Except for the diatomic species, no experimental values for RP are available yet.

Original languageEnglish
Pages (from-to)143-149
Number of pages7
JournalJournal of Molecular Structure
Volume556
Issue number1-3
DOIs
Publication statusPublished - Dec 12 2000

Keywords

  • Ab initio calculations
  • Heats of formation
  • Phosphanylidenes
  • Phosphinidenes
  • Thermochemistry

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

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