PP-Rotation, P-Inversion and Metathesis in Diphosphines Studied by DFT Calculations: Comments on Some Literature Conflicts
Abstract
:1. Introduction
2. Results and Discussion
2.1. Rotational Isomerization
2.2. Stereomutation by Pyramidal Inversion
2.3. Stereomutation by Metathesis Self-Reaction
3. Methods
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Technique | Conclusion |
---|---|
Raman spectroscopy [18] | 60:40 gauche:anti (liquid) |
IR spectroscopy [19] | 60:40 gauche:trans |
Electron diffraction | exclusively distorted trans |
Photoelectron spectroscopy | 16:84 gauche:trans |
VT PE spectroscopy | trans more stable than gauche 2.1 ± 0.4 kJ/mol |
MS fragmentation analysis | exclusively trans |
Computational | trans more stable than gauche 6.1 vs. 5.4 kJ/mol: MP2 6-311+G* vs. B3LYP 6-311+G* |
Compound | Compound | anti b | eclipsed (TS) c | gauche b | syn (TS) c | ||
H4P2 | 1 | 0.0 | 3.9 | 0.9 | 15.0 | ||
Me4P2 | 2 | 0.0 | 13.0 | 4.4 | 29.8 | ||
(CF3)4P2 | 3 | 0.0 | 7.7 | 1.5 | 45.9 | ||
Ph4P2 | 4 | 0.0 | 22.8 | 11.1 | 52.6 | ||
Me2P–(CF3)2P | 5 | 1.0 | 11.0 | 0.0 | 31.2 | ||
Me2P–Ph2P | 6 | 0.0 | 13.6 | 5.9 | 42.9 | ||
Me(CF3)P–P(CF3)Me | 7-meso | 0.0 | 9.1 | 2.8 | 41.4 | ||
MePhP–PPhMe | 8-meso | 0.0 | 15.2 | 4.5 | 37.4 | ||
Compound | Compound | anti | eclipsed (R) | gauche (R) | syn | gauche (Me) | eclipsed (Me) |
Me(CF3)P–P(CF3)Me | 7-dl | 1.1 | 23.7 | 8.6 | 35.7 | 0.0 | 5.1 |
MePhP–PPhMe | 8-dl | 0.0 | 16.2 | 4.1 | 29.5 | 5.3 | 17.6 |
Compound | This Work: anti:gauche Boltzmann Distribution at B3LYP/6-31G* | Literature Values anti:gauche |
---|---|---|
H4P2 (1) | 59:41 | - |
Me4P2 (2) | 86:14 | 84:16 [25] |
(CF3)4P2 (3) | 64:36 | 85:15 ±10 [22] 90:10 [25] |
Ph4P2 (4) | 99:1 | - |
Compound | Compound | Inversion (R) | ||
H4P2 | 1 | 110.7 | ||
Me4P2 | 2 | 114.0 | ||
(CF3)4P2 | 3 | 100.9 | ||
Ph4P2 | 4 | 84.6 | ||
Compound | Compound | Inversion (R) | Inversion (Me) | |
Me2P–(CF3)2P | 5 | 106.4 | 100.8 | |
Me2P–Ph2P | 6 | 86.5 | 106.9 | |
Compound | Compound | (R)-gauche-meso a | (R)-gauche (Me)-dl b | (R)-gauche (X)-dl c |
Me(CF3)P–P(CF3)Me | 7 | 102.8 | 107.4 | 99.1 |
MePhP–PPhMe | 8 | 103.1 | 100.8 | 101.8 |
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Molloy, A.D.; Sánchez-Sanz, G.; Gilheany, D.G. PP-Rotation, P-Inversion and Metathesis in Diphosphines Studied by DFT Calculations: Comments on Some Literature Conflicts. Inorganics 2016, 4, 36. https://doi.org/10.3390/inorganics4040036
Molloy AD, Sánchez-Sanz G, Gilheany DG. PP-Rotation, P-Inversion and Metathesis in Diphosphines Studied by DFT Calculations: Comments on Some Literature Conflicts. Inorganics. 2016; 4(4):36. https://doi.org/10.3390/inorganics4040036
Chicago/Turabian StyleMolloy, Adam D., Goar Sánchez-Sanz, and Declan G. Gilheany. 2016. "PP-Rotation, P-Inversion and Metathesis in Diphosphines Studied by DFT Calculations: Comments on Some Literature Conflicts" Inorganics 4, no. 4: 36. https://doi.org/10.3390/inorganics4040036