Topic
Phosphorine
About: Phosphorine is a research topic. Over the lifetime, 32 publications have been published within this topic receiving 240 citations.
Papers
TL;DR: None of the combinations of the functionals and the dispersion correction methods can reproduce well the CCSD(T) level interaction potentials of all the complexes.
Abstract: Intermolecular interaction potentials for benzene, propane, perfluoromethane, furan, thiophene, selenophene, pyridine, phosphorine dimers and benzene–methane, benzene–chlorobenzene, benzene–bromobenzene complexes were calculated using the BLYP, B97 (B98), BP86, BPBE, PBE, PW91, B3LYP, B3PW91, BMK, PBE1PBE, APF, ωB97 (ωB97X), CAM-B3LYP, LC-ωPBE, B2PLYP, mPW2PLYP, TPSS, M06L, M05, M052X, M06, M062X and M06HF functionals with Grimme's dispersion correction methods of D2, D3 and D3BJ versions. The calculated potentials were compared with the CCSD(T) level potentials to evaluate the accuracy of the dispersion corrected DFT methods for calculating the intermolecular interaction energies of hydrocarbon molecules and molecules including heteroatoms (N, P, O, S, Se, F, Cl and Br). The performance of the calculations depends strongly on the choice of the functional and the dispersion correction method. None of the combinations of the functionals and the dispersion correction methods can reproduce well the CCSD(T) level interaction potentials of all the complexes. The improvement of the functionals from GGA to hybrid GGA, meta GGA or meta hybrid GGA is not essential for improving the performance. The significant functional dependence suggests that the scaling factors, which were determined for each functional by fitting, are the cause of the dependence. The performance of the calculations of hydrocarbon molecules is much better than that of the molecules including heteroatoms. A smaller number of molecules including heteroatoms were used for the reference data of the fitting compared with hydrocarbon molecules, which might be one of the causes of the worse performance of the calculations of molecules including heteroatoms.
96 citations
TL;DR: Using photochemical excitation or ligand displacement reactions, 2,4,6-triphenylphosphorine-metal pentacarbonyls and cis -bis(2,4-6-triangulatedphosphoricine)-metal tetracarbonyl of chromium, molybdenum and tungsten have been prepared.
72 citations
TL;DR: Pentacarbonyl(2,4,6-triphenylphosphorine)chromium as discussed by the authors is a monoclinic space group P21/c with four molecules in the unit cell.
Abstract: Pentacarbonyl(2,4,6-triphenylphosphorin)chrom(0) kristallisiert monoklin in der Raumgruppe P21/c mit vier Molekulen in der Elementarzelle. Die Pentacarbonylchromgruppe ist so an das Phosphoratom des Phosphorin-Ringes koordiniert, das die Cr–P–Bindung um 8° gegen die Ringebene geneigt ist. Die Cr–P–Bindung ist mit 2.37 A, relativ kurz. Der Phosphorin-Ring ist planar. Seine Geometrie stimmt weitgehend mit der P-unsubstituierter Phosphorine uberein.
Heteroaromatic Complex Ligands. The Crystal Structure of Pentacarbonyl(2,4,6-triphenylphosphorine)chromium(0)
Pentacarbonyl(2,4,6-triphenylphosphorine)chromium crystallizes in the monoclinic space group P21/c with four molecules in the unit cell. The pentacarbonyl chromium moiety is coordinated to the phosphorus atom of the phosphorine ring in such a way that the Cr–P bond is inclined by an angle of 8 degrees out of the ring plane. The Cr–P bond of 2.37 A is relatively short. The phosphorine ring is planar. Its geometry closely resembles that of P-unsubstituted phosphorines.
55 citations
TL;DR: Theoretical results for the gas-phase proton affinities of phosphaethyne and phosphabenzene have been obtained from ab initio SCF calculations employing analytic gradient techniques for geometry optimization.
Abstract: Theoretical values for the gas-phase proton affinities (PA’s) of phosphaethyne, phosphaethene, and phosphabenzene have been obtained from ab initio SCF calculations employing analytic gradient techniques for geometry optimization. The sensitivity of the results to the choice of basis set and to the inclusion of correlation is discussed. The PA’s for P-site and C-site protonation are found to be nearly equal in both phosphaethene and phosphabenzene at the split-valence SCF level; however, polarization functions and electron correlation both act to favor P-site protonation over C-site protonation, resulting in an isomerization energy of approximately 50 kJ mol-’. By contrast we find C-site protonation to be strongly favored over P-site protonation for phosphaethyne even at the split-valence SCF level. Comparisons are made to computed and observed PA’s both for saturated C-P systems and for saturated and unsaturated C-N systems. The computed order of basicities, H3CPH2 > C5H5P > PH3 > H2CPH > HCP (C-site), differs from that for the corresponding N systems, namely, C5HSN > H3CNH2 > HICNH = NH3 > HCN, not only in the lower position of C5H5P, as is well-known, but also in the lower position of H2CPH.
44 citations
TL;DR: N-Mesitylene sulfonyl and N-tosyl aziridines have been identified as effective electrophiles in alkylation reactions of carbon acids catalyzed by the organic phosphorine base BEMP, with yields of up to 99% for a range of pro-nucleophiles under mild reaction conditions.
15 citations
Related Topics (5)
Performance Metrics
| Year | Papers |
|---|---|
| 2021 | 1 |
| 2020 | 1 |
| 2018 | 1 |
| 2010 | 1 |
| 2008 | 3 |
| 2005 | 2 |