On the Use of Triarylsilanols as Catalysts for Direct Amidation of Carboxylic Acids
DOI: 10.14469/hpc/12480 Metadata
Created: 2023-04-18 07:34
Last modified: 2023-07-12 07:13
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Co-author: D. Christopher Braddock Co-author: Rabia Qamar
Description
To estimate the relative free energies of the species involved in the proposed catalytic cycle for a typical set of substituents (scheme), density functional calculations were carried out at both the B3LYP+GD3+BJ and ?B97XD dispersion-corrected levels1, using a Def2-TZVPP basis set2, a CPCM model3 for continuum solvation and an accurate 175,974 two-electron integral grid for first-row atoms and 250,974 for Si. Initial optimized geometries were obtained at the PM7 dispersion-corrected semiempirical level.4 Full input and output files are available as a FAIR data repository collection.5 Free energies are calculated at 298K for a standard state of 1 atm and can be converted to 384K and 4 atm. by recovering the checkpoint file from the repository and rerunning using the keywords # geom=checkpoint freq(readfc) pressure=4.0 temp=383.85 1 Grimme, S. Ehrlich and L. Goerigk, “Effect of the damping function in dispersion corrected density functional theory,” J. Comp. Chem. 32 (2011) 1456-65. DOI: 10.1002/jcc.21759 2 F. Weigend, “Accurate Coulomb-fitting basis sets for H to Rn,” Phys. Chem. Chem. Phys., 8 (2006) 1057-65. DOI: 10.1039/B515623H 3 M. Cossi, N. Rega, G. Scalmani, and V. Barone, “Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model,” J. Comp. Chem., 24 (2003) 669-81. DOI: 10.1002/jcc.10189 4 J. J. P. Stewart, “Optimization of parameters for semiempirical methods VI: more modifications to the NDDO approximations and re-optimization of parameters,” J. Molec. Modeling 19 (2013) 1-32. DOI: 10.1007/s00894-012-1667-x 5 Authors, Imperial College Research Data Repository, 2023, DOI: 10.14469/hpc/12480
Members
| DOI | Description |
|---|---|
| 10.14469/hpc/12481 | Water, B3LYP+GD3+BJ/Def2-TZVPP, Toluene, G = -76.468109 |
| 10.14469/hpc/12485 | p-MeArCO2H.H2N-CH2-Ph complex, 11, B3LYP+GD3+BJ/Def2-TZVPP, Toluene, G = -826.528061 |
| 10.14469/hpc/12486 | p-MeArCO2H.H2N-CH2-Ph complex as a salt, 11, B3LYP+GD3+BJ/Def2-TZVPP, Toluene, G = -826.528062 |
| 10.14469/hpc/12487 | Hexaphenyldisilyl ether, 10, B3LYP+GD3BJ/Def2-TZVPP, G = -2044.592096 |
| 10.14469/hpc/12490 | Triphenylsilamine, species 9, G = -1350.310640 |
| 10.14469/hpc/12492 | Hexaphenyldisilyl ether, 10, B3LYP+GD3BJ/Def2-TZVPP, C2-symmetry, G = -2044.591456 |
| 10.14469/hpc/12493 | Phenylacetic acid/p-Me-Benzylamine amide monomer, 3a, B3LYP+GD3BJ/Def2-TZVPP, Toluene, iso G = -750.070576 |
| 10.14469/hpc/12494 | Phenylacetic acid/p-Me-Benzylamine amide monomer, 3a, B3LYP+GD3BJ/Def2-TZVPP, Toluene, G = -750.064199 |
| 10.14469/hpc/12500 | Phenylacetic acid/p-Me-Benzylamine amide dimer, 3a, B3LYP+GD3BJ/Def2-TZVPP, Toluene, G =-1500.134341 |
| 10.14469/hpc/12499 | Silyl-imidate 13, B3LYP+GD3+BJ/Def2-TZVPP, toluene, G = -2194.351707 |
| 10.14469/hpc/12510 | Phenylacetic acid/p-Me-Benzylamine amide monomer, 3a, B3LYP+GD3BJ/Def2-TZVPP, Toluene, iso, G = -750.064201 |
| 10.14469/hpc/12511 | p-methylbenzylamine, wB97XD/Def2-TZVPP, toluene, 2a, G = -366.107652 |
| 10.14469/hpc/12512 | Triphenylsilamine, species 9, wB97XD/Def2-TZVPP, G = -1350.310640 |
| 10.14469/hpc/12516 | Silyl-imidate 13, wB97XD/Def2-TZVPP, toluene, |
| 10.14469/hpc/12538 | Silyl-imidate 13, B3LYP+GD3+BJ/Def2-TZVPP, toluene, without accompanying acid, |G = -1734.096138 |
| 10.14469/hpc/12546 | 14: Acyl imidate, wB97XD, G = -1133.312128 |
| 10.14469/hpc/12547 | 14: acetimidic anhydride, B3LYP=GD3+BJ, G = -1133.815152 |
| 10.14469/hpc/12549 | 15: Diacyl amine, iso E = -1134.1910, G = -1133.836498 |
| 10.14469/hpc/12551 | 15: Diacyl amine, iso 2, G = -1133.837277 |
| 10.14469/hpc/12553 | 14: acetimidic anhydride, iso, b3lyp+GD3+BJ, iso, G = -1133.818400 |
| 10.14469/hpc/12555 | 16: Triphenylsilyl acyl amine, E = -1734.59071, G =-1734.102445 |
| 10.14469/hpc/12556 | 16: Triphenylsilyl acyl amine, wB97XD, G = -1733.407058 |
| 10.14469/hpc/12557 | 16: Triphenylsilyl acyl amine, iso, G = -1734.101205 |
| 10.14469/hpc/12558 | 16: Triphenylsilyl acyl amine, iso, wB97XD, G = -1733.408545 |
| 10.14469/hpc/12559 | 15: Diacyl amine, E = -1134.194690, G = -1133.839568 ==> -1133.834160 |
| 10.14469/hpc/12563 | 16: Triphenylsilyl acyl amine, wB97XD E = -1733.901578 ==> -1733.9038 |
| 10.14469/hpc/12564 | 15: Diacyl amine, G = -1133.839568 ==> -1133.834150 |
| 10.14469/hpc/12573 | Water, B3LYP+GD3+BJ/Def2-TZVPP, Toluene, G = -76.474598 @ temp=383.85 |
| 10.14469/hpc/12496 | triphenylsilanol in toluene + phenylacetate, 7, B3LYP+GD3BJ/Def2-TZVPP, G = -1444.306832 |
| 10.14469/hpc/12483 | phenylacetic acid dimer, 1a, B3LYP+GD3+BJ/Def2-TZVPP, toluene, G = -920.511769 ½ G = -460.2558845 |
| 10.14469/hpc/12540 | Silyl-imidate 13, B3LYP+GD3+BJ/Def2-TZVPP, toluene, iso G = -2194.354885 |
| 10.14469/hpc/12562 | 16: Triphenylsilyl acyl amine, G =-1734.102445 ==> -1734.103157 |
| 10.14469/hpc/12548 | 15: Diacyl amine, G = -1133.839568 |
| 10.14469/hpc/12554 | 14: acetimidic anhydride, iso, b3lyp+GD3+BJ, iso, G = -1133.818400 |
| 10.14469/hpc/12495 | Triphenylsilaminium-carboxylate-salt, 8 G = -1810.563502 |
| 10.14469/hpc/12491 | Phenylacetic acid/p-Me-Benzylamine amide monomer, 3a, B3LYP+GD3BJ/Def2-TZVPP, Toluene, G = -750.070659 |
| 10.14469/hpc/12484 | triphenylsilanol in toluene, 4, B3LYP+GD3BJ/Def2-TZVPP, G = -1060.522278 |
| 10.14469/hpc/12482 | p-methylbenzylamine, 2a, B3LYP+GD3+BJ/Def2-TZVPP, toluene, G = -366.272639 |
| 10.14469/hpc/12574 | phenylacetic acid monomer, 1a, B3LYP+GD3+BJ/Def2-TZVPP, toluene, G = -460.252456@298, -460.266112@383.85 (½ G = -920.534097/2 = -460.2670485 for dimer @ 383.85K) |
| 10.14469/hpc/12513 | phenylacetic acid dimer, 1a, wB97XD/Def2-TZVPP, toluene, G = ½ -460.061684 G = -920.1233 |
| 10.14469/hpc/12498 | Phenylacetic acid/p-Me-Benzylamine amide dimer, 3a, B3LYP+GD3BJ/Def2-TZVPP, Toluene, G = -1500.134125 ½ -750.0670625 vs -750.070659 for monomer amide |
| 10.14469/hpc/12575 | phenylacetic acid monomer, 1a, wB97XD/Def2-TZVPP, toluene, G = -460.072866 @ 383.85 (-460.07274 for dimer@383.85) |
| 10.14469/hpc/12542 | Silyl-imidate 13, wB97XD/Def2-TZVPP, toluene, iso G = -2193.465012 |
| 10.14469/hpc/12515 | Hexaphenyldisilyl ether, 10, wB97XD//Def2-TZVPP, C2-symmetry, G = -2043.844066 |
| 10.14469/hpc/12541 | Triphenylsilaminium-carboxylate-salt, 8 wB97XD, G = -1809.843808 |
| 10.14469/hpc/12518 | triphenylsilanol in toluene + phenylacetate, 7,wB97XDJ/Def2-TZVPP, G =-1443.752531 |
| 10.14469/hpc/12509 | Phenylacetic acid/p-Me-Benzylamine amide monomer, 3a, wB97XD/Def2-TZVPP, Toluene, iso, G =-749.732088 |
| 10.14469/hpc/12514 | triphenylsilanol in toluene, 4, wB97XD/Def2-TZVPP, G = -1060.136607 |
| 10.14469/hpc/12552 | 14: acetimidic anhydride, iso, wB97XD, G = -1133.315749 |
| 10.14469/hpc/12550 | 15: Diacyl amine, wB97XD, G = -1133.337968 |
| 10.14469/hpc/12577 | mixed acid/amide complex, B3LYP+GD3+BJ/Def2-TZVPP, G = -1210.322481 (@298), -1210.349696 (@383.85K) |
| 10.14469/hpc/12590 | 17: triphenylsilyl ester 5-coordinate with amide, wB97XD G = -2193.479580 |
| 10.14469/hpc/12581 | WENBOG, B3LYP+GD3+BJ/Def2-TZVPP rSi-O = 2.620 |
| 10.14469/hpc/12587 | WENBOG, B3LYP+GD3+BJ/Def2-QZVPP, RSi-O = 2.578 |
| 10.14469/hpc/12589 | Water, wB97XD/Def2-TZVPP, Toluene, @383.85K G = -76.448444 |
| 10.14469/hpc/12579 | Water, wB97XD/Def2-TZVPP, Toluene, G |
| 10.14469/hpc/12588 | Water, wB97XD/Def2-TZVPP, Toluene, = G = -76.441958 |
| 10.14469/hpc/12585 | Water, B3LYP+GD3+BJ/Def2-TZVPP, Toluene, G = -76.474609 @ temp=383.85 |
| 10.14469/hpc/12615 | 17: triphenylsilyl ester 5-coordinate with amide, G = (384K, 1 atm) -2194.413086 |
| 10.14469/hpc/12497 | FAIR Data Table showing relative free energies of species 1-17 at 298K and 1 atm. pressure |
Associated DOIs
| Current dataset ... | DOI | Description |
|---|---|---|
| References | 10.1021/acs.joc.3c00585 | On the Use of Triarylsilanols as Catalysts for Direct Amidation of Carboxylic Acids |
| isReferencedBy | 10.1021/acs.joc.3c00585 | Silicon-containing catalysts and reagents for the direct amidation of carboxylic acids |
| References | 10.25560/78224 | Silicon-containing catalysts and reagents for the direct amidation of carboxylic acids |