A Thermodynamic assessment of the reported room-temperature chemical synthesis of C2
DOI: 10.14469/hpc/7185 Metadata
Created: 2020-05-11 11:35
Last modified: 2022-08-31 10:48
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Description
Chemical formation of C2 from an alkynyl iodonium salt precursor is calculated to be strongly endo-energetic, in contrast to the reported chemical synthesis and trapping which is facile at room temperatures. If C2 is to be formed at such temperatures, a mechanism to counter the unfavourable thermodynamic energies must be identified.
Members
| DOI | Description |
|---|---|
| 10.14469/hpc/7246 | CH3-I-CC CCSD(T)/Def2-TZVPPD/SCRF=DCM E -412.8495128 (reactant) TS migration from reactant E = 412.7893362 (13.7 below CC + IMe) G = -412.777622 |
| 10.14469/hpc/7245 | CH3-CC-I CCSD(T)/Def2-TZVPPD/SCRF=DCM Product iodoacetylene E = -412.98136 G = -412.963264 ΔG = -79.1 |
| 10.14469/hpc/7180 | CH3-I CCSD(T)/Def2-TZVPP/SCRF=DCM G = -336.965647 Sum = -412.765304 |
| 10.14469/hpc/7179 | CC CCSD(T)/Def2-TZVPP/SCRF=DCM G = -75.799657 |
| 10.14469/hpc/7196 | CH3-I-CC CCSD(T)/Def2-TZVPP/SCRF=DCM E = -412.8437462 |
| 10.14469/hpc/7182 | CH3-I CCSD/Def2-TZVPP/SCRF=DCM G = -336.948964 Sum of products -412.715133 |
| 10.14469/hpc/7181 | CC CCSD/Def2-TZVPP/SCRF=CPM G = -75.766169 |
| 10.14469/hpc/7213 | CC CCSD(T)/Def2-TZVPPD/CPCM=DCM freq G = -75.800442 Tight convergence |
| 10.14469/hpc/7197 | CH3-I-CC CCSD(T)/Def2-TZVPPD/SCRF=DCM ΔG = -412.837278, ΔΔG = 42.5 + 4.6 = 47.1 |
| 10.14469/hpc/7204 | CH3-I-CC CCSD(T)/Def2-TZVPP/SCRF=DCM G = -412.831473 DG = 41.4, corrected = 46.1 |
| 10.14469/hpc/7193 | CH3-I-CC CCSD(T)/Def2-TZVPPD/SCRF=DCM ΔE = 51.5 + 4.6 = 56.1 |
| 10.14469/hpc/7183 | CH3-I-CC CCSD/Def2-TZVPP/SCRF=DCM G = -412.791006 ΔG = 47.6 (16.7 solvation) |
| 10.14469/hpc/7188 | CC CCSD(T)/Def2-TZVPPD/CPCM=DCM E = -75.7863285, G = -75.800442 |
| 10.14469/hpc/7189 | CH3-I CCSD(T)/Def2-TZVPPD/CPCM=DCM E = -336.9811369, G = -336.969115 Gsum = -412.769557 |
| 10.14469/hpc/7593 | Bimolecular MeI+ CCIMe, TS C2h CCSD(T)/Def2-SVPD/SCRF=DCM E = -748.8119682 (-748.7838813) DE = 17.6 |
| 10.14469/hpc/7580 | Bimolecular MeI+ CCIMe TS C2h CCSD(T)/Def2-TZVPPD/SCRF=DCM E = -749.7885067 (-749.7486023) DE = 25.0 |
| 10.14469/hpc/7199 | Energies/Enthalpies for HCCH => HCC• + H• => CC + H• CCSD(T)/Def2-TZVPP and Def2-TZVPPD |
Associated DOIs
| Current dataset ... | DOI | Description |
|---|---|---|
| References | 10.1038/s41467-021-21433-8 | Published in Nature Communications |
| References | 10.1038/s41467-021-21433-8 | Published article: A Thermodynamic assessment of the reported room-temperature chemical synthesis of C2 |
| References | 10.14469/hpc/7198 | Enthalpies for HCCH => HCC• + H• => CC + H• wB97XD/Def2-SVO |
| References | 10.26434/chemrxiv.12237980.v2 | Rzepa, Henry S. (2020): A Thermodynamic assessment of the reported room-temperature chemical synthesis of C2. ChemRxiv. Preprint. |