THE EXPERIMENTAL AND THEORETICAL THERMOCHEMISTRY OF P-H-CONTAINING ORGANOPHOSPHORUS COMPOUNDS

Abstract

The thermochemistry of primary, secondary phosphines, RPH ₂ , R ₂ PH, and hydrophosphorylic compounds, (RO) ₂ P(O)H, of the different spatial structure is presented in this review. The values of the vaporization, solvation, and formation enthalpies (for nearly 100 compounds) belonging to the above mentioned classes of compounds are determined. For these aims of the Trouton, Wadso equations, and the molar topological solvation index approaches, and half-empirical Solomonov-Konovalov equation (ΔH_vap/kJ mol ¹ = ΔH _soln (alkane) + 4.39 + 1.05 MR _D ), have been used. The questions of solvation, tautomeric transformations, complex formation or the hydrogen bonding formation have been used also. The heats of the addition reactions of hydrophosphorylic compounds are presented as well. The group contributions into the vaporization and formation enthalpies for primary and secondary phosphines, [-PH ₂ , > PH], are calculated and discussed.

Keywords:

• Formation enthalpies
• heat capacity
• heat of reaction
• hydrophosphorylic compounds
• molar refraction
• phosphines
• solvation
• topological solvation index
• vaporization

Notes

^a Data taken from Refs. 2, 46, 47.

^b Experimental MR_D values are listed for compounds (7–9, 13–19, 31, 35–37, 44, 50, 53); for other compounds the MR_D values were calculated using the group additive scheme; corrections to the MR_D values were introduced for branched R. ⁴⁸

^c Experimental μ values are listed for compounds (3–7, 13, 25, 26, 31–33, 48, 49); ^48,50 otherwise the dipole moments were calculated by the molecular mechanics (MMX) method.

^d The ΔH _vap values for these compounds were calculated from the temperature dependence of vapor pressure. ⁴⁸

^e Data taken from Ref. 51.

^f Data taken from Ref. 1.

^a Calculated by the authors.

^a The magnitudes can be easy calculated this the use of Figure 1; error of Δ H ^o _f in condensed phase has been taken as equal to the error of Δ H _vap (see Table 3).

^a Calculated for hexane using Eq. 11; calculated for CCl₄ using Eq. 19.

^b Δ H _vap = 49.3 kJ mol^{−1 69}.

^a Has been determined to be no worse than ± 0.3–0.8 kJ mol^{− 1}.

^b For the acid (61) 2-methoxy-4,5-benzo-1,3,2-dioxaphospholane has been used as a model compound with P(III) atom.

^a Calculated using the thermochemical data of reaction PCl₃ + (EtO)₂CHMe. ⁸⁹

^b Data from Ref. 90.

^a The experimental error were calculated using the errors of solution and partial hydrolysis.

^b Data from Ref. 69.

^a Calculated using the equation Δ H _solv = 11.7 + 1.08 MR_D from Table V.

^a Recalculated values.