ISSN:
1434-1948
Schlagwort(e):
Ab initio calculations
;
Ionization potentials
;
Phosphorus
;
Heterocycles
;
Small ring systems
;
Chemistry
;
General Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Ab initio quantum chemical calculations have been used to explore the P3H3 potential energy surface focussing on the ring-chain rearrangements of the three-membered ring in (PH)3 (1), the parent triphosphirane. Relative energies between stationary points were estimated using the QCISD(T)/6-311G(d,p) method based on MP2/6-31G(d,p) geometries and corrected for zero-point contributions. Ring strain, proton affinities, ionization and excitation energies and heats of formation have been evaluated using larger basis sets, e.g. 6-311++G(3df,2p). The cyclic trans-triphosphirane (1a) is the most stable P3H3 isomer and lies about 40 kJ/mol below the open-chain phosphanyldi-phosphene (H2P-P=PH). The decrease of ring strain in three-membered rings when CH2 is replaced by PH is confirmed. Triphosphirane 1a is a virtually strain-free ring and even gains some stabilization relative to three separate P-P single bonds. The reduced ring strain also helps diminish the phosphorus inversion barrier to 224 kJ/mol compared to the monocyclic isomers of (CH2)(PH)2 and (CH2)2(PH). Compound 1a follows a pure ring-opening or a 1,2-hydrogen shift rather than a combined motion pathway, in fundamental contrast with corresponding processes of diphosphirane and phosphirane. This is due to the existence of an open-chain P3H3 phosphorane intermediate stabilized by allylic conjugation. The pericyclic ring-opening of 1a is the most favored process but the energy barrier in the gas phase is about 180 kJ/mol high. Electron density is largely delocalized within the three-membered P3 ring not only in the C3v-symmetric 1b (all-cis) but also in 1a (Cs). The proton affinity of 1a is similar to that of PH3. The proton affinities decrease with n in cyclo-(CH3)3 -n(PH)n and their values were obtained: PA(1a) = 777 ±10, PA(diphosphirane) = 799 ±10 and PA(phosphirane) = 802 ±10 kJ/mol. Heats of formation are evaluated as follows (ΔH°f0 at 0 K in kJ/mol): 1a, 70 ±10; cyclo-(PH)2(PH2)+ (protonated 1a), 821 ±10; diphosphirane, 85 ±10; cyclo-(CH2)(PH)(PH2)+ (protonated diphosphirane), 814 ±10; phosphirane, 86 ±10; and protonated phosphirane, 812 ±10 kJ/mol. All P rings remain cyclic following ionization to the radical cations. Adiabatic ionization energies (IEa) are estimated as: 1a and diphosphirane, 9.3 ±0.3 eV and phosphirane 9.5 ±0.3 eV. The first UV absorption band shifts toward the longer wavelength region on going from phosphirane to 1a. The GIAO/B3LYP computed magnetic shieldings for 1a and related molecules reveal a clear relationship between the narrow bond angles in the rings and their unusually strong magnetic shielding. The similarity of the predicted 31P-NMR signals in 1a and its heteroanalog diphosphirane, (CH2)(PH)2, can be rationalized in terms of a compensation of the carbon-substituent effect (downfield shift) and the bond-bending effect imposed by the ring (upfield shift).
Zusätzliches Material:
5 Ill.
Materialart:
Digitale Medien
Permalink
