DOI: 10.14469/hpc/7616 Metadata

Created: 2020-12-06 16:14

Last modified: 2021-05-29 20:21

Author: Henry Rzepa

License: Creative Commons: Public Domain Dedication 1.0

Funding: (none given)

Description

Recent lively debates about the nature of the quadruple bonding in the diatomic species C2 have been heightened by recent suggestions of molecules in which carbon may be similarly bonded to other elements. The desirability of having methods for generating such species at ambient temperatures and in solution in order to study their properties may have been realized by a recent report of the first chemical synthesis of free C2 itself under mild conditions. The method involved unimolecular fragmentation of an alkynyl zwitterion 2 as generated from the precursor 1, resulting in production and then trapping of free C2 at ambient temperatures rather than the high temperature gas phase methods normally employed for C2 generation. Here, alternative mechanisms are proposed for this reaction based on DFT calculations involving bimolecular 1,1- or 1,2-iodobenzene displacement reactions from 2 directly by galvinoxyl radical, or hydride transfer from 9,10-dihydroanthracene to 2. These mechanisms result in the same trapped products as observed experimentally, but unlike that involving unimolecular generation of free C2, exhibit calculated free energy barriers commensurate with the reaction times observed at room temperatures. The relative energies of the transition states for 1,1 vs 1,2 substitution provide a rationalisation for the observed isotopic substitution patterns. The same mechanism also provides an energetically facile path to polymeric synthesis of carbon rich species by extending the carbon chain attached to the iodonium group, eventually resulting in formation of amorphous carbon and discrete molecules such as C60.

Members

DOI	Description
10.14469/hpc/7687	CC-IPh + Galvinoxyl 1,2-TS, Def2-SVPD G = -1883.404654
10.14469/hpc/7688	CC-IPh + Galvinoxyl 1,1-TS, Def2-SVPD, G = -1883.401400
10.14469/hpc/7691	F(-) + CCIPh, wB97XD/Def2-TZVPPD, SCRF=dichloromethane Reactant G = -705.385855
10.14469/hpc/7698	CC M062X/Def2-TZVPPD/CPCM=DCM
10.14469/hpc/7699	Bimolecular TS C2h M062X/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7693	PhICC + CCIPh 1,2 -TS IRC
10.14469/hpc/7701	CH3-I M062X/Def2-TZVPPD/CPCM=DCM
10.14469/hpc/7700	CH3-I-CC M062X/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7702	CC B2PLYPD3/Def2-TZVPPD/CPCM=DCM
10.14469/hpc/7695	PhI + 9,10-dihydroanthracene, Cs G = -1069.139646
10.14469/hpc/7703	Bimolecular TS C2h B2PLYPD3/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7706	Bimolecular TS C2h b3lyp/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7697	PhICC + 9,10-dihydroanthracene, 1,2 Saddle=1, RHF G = 1145.008883
10.14469/hpc/7707	CC B3LYP+GD3BJ/Def2-TZVPPD/CPCM=DCM
10.14469/hpc/7972	Reaction between Dichloromethane and CC.
10.14469/hpc/7709	CH3-I-CC B3LYP+GD3+BJ/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7710	CH3-I-CC wB97XD/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7727	CC-IPh + Galvinoxyl 1,1-TS, Def2-SVPD, G = -1883.401400 => gas phase G = -1883.377039
10.14469/hpc/7728	PhICCCC + CCCCIPh, 1,4-TS, C1 G = -1362.126689, DG = 27.3
10.14469/hpc/7712	Bimolecular TS C2h wB97XD/Def2-TZVPPD/SCRF=DCM E = -751.361189392 DE = 28.5 G = -751.320309 DG = 35.2
10.14469/hpc/7729	PhICC + CCCCCCIPh 1,2 -TS Def2-SVPD/CPCM=DCM, G = -1362.136592
10.14469/hpc/7711	CH3-I wB97XD/Def2-TZVPPD/CPCM=DCM E = -337.704325229 == -751.2745250139; G = -337.692199 == -751.264282
10.14469/hpc/7730	PhICCIPh + CC as new mechanism for forming C2 G = -1209.920739 DG = +86.6 compared to 2*PhICC
10.14469/hpc/7713	CC,wB97XD/Def2-SVPD/SCRF=DCM, E = -75.7780175117 G = -75.791993
10.14469/hpc/7731	PhICC + CCCCCCIPh reactant, E = -1362.33225, G = -1362.175663
10.14469/hpc/7714	MeI wB97XD/Def2-SVPD DCM E = -337.646958184, 2* = -675.293916368 ==-751.0719338797; G = 2*-337.635095 = -675.27019 == -751.062183
10.14469/hpc/7733	PhICC + CCCCCCIPh, 1,1-TS, one Ph group rotated, Cs symmetry G = -1362.153211 DDG = 14.1
10.14469/hpc/7716	CH3-I PBEQIDH/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7734	PhICC + CCCCCCIPh, 1,1-TS G = -1362.154439 DG = 13.3
10.14469/hpc/7717	CH3-I-CC PBEQIDH/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7718	Bimolecular TS C2h PBEQIDH/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7715	CC PBEQIDH/Def2-TZVPPD/CPCM=DCM
10.14469/hpc/7736	pentafluoroPhICC + phenoxy, reactant, Def2-SVPD, SCRF=DCM, G = -1407.185828
10.14469/hpc/7705	CH3-I B2PLYPD3/Def2-TZVPPD/CPCM=DCM
10.14469/hpc/7708	CH3-I B3LYP+GD3+BJ/Def2-TZVPPD/CPCM=DCM
10.14469/hpc/7704	CH3-I-CC B2PLYPD3/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7738	pentafluoroPhICC + phenoxy,1,1-TS, Def2-SVPD, SCRF=DCM, G = -1407.151796, DG = 21.4
10.14469/hpc/7739	Pentafluorophenyl-I-CC, Def2-SVPD, SCRF=DCM, G = -1100.732513
10.14469/hpc/7741	PhICCCC + CCCCIPh, reactant, C2h, G = -1362.170263
10.14469/hpc/7755	Galvinoxyl alone, Def2-SVPD, SCRF=DCM, G = -1278.418870
10.14469/hpc/7762	phenoxy radical, wB97XD/Def2-SVPD G = -306.455338
10.14469/hpc/7763	PhICC + CCCCIPh, branched mode to produce C5 chain, anti, G = -1286.077648
10.14469/hpc/7766	PhICC + CCCCIPh, branched mode to produce C5 chain, syn G = -1286.086804
10.14469/hpc/7769	PhICC + CCCCCCCCIPh, 1,1-TS Def2-SVPD/CPCM=DCM, G = -1438.214217
10.14469/hpc/7770	PhICC + CCCCCCCCIPh reactant, Def2-SVPD/CPCM=DCM, G = -1438.233118
10.14469/hpc/7771	PhICC+CCIPh-1,2 G = -1210.034333, => syn G = -1210.030662
10.14469/hpc/7776	PhICC+CCCCIPh-1,2 G = -1286.079175 => syn, G = -1286.082736
10.14469/hpc/7773	PhICC + CCCCCCIPh 1,2 -TS Def2-SVPD/CPCM=DCM, G = -1362.136592 => branched syn G = -1362.148139
10.14469/hpc/7779	Galvinoxyl + IPh + CC, Def2-SVPD, rotamer, - G = -1807.553360
10.14469/hpc/7788	PhBrCC + CCBrPh 1,2, Def2-SVPD/SCRF=DCM, -TS, G = -5762.262426, DG = 13.3
10.14469/hpc/7790	PhAtCC + CCAtPh 1,2 -TS C2h, G = -1139.591210
10.14469/hpc/7792	PhBrCC + CCBrPh 1,2, Def2-SVPD/SCRF=DCM, Reactant, G = -5762.283563
10.14469/hpc/7793	PhAtCC + CCAtPh 1,2 -Reactant C2h,, G = -1139.618899
10.14469/hpc/7794	PhBrCC + CCBrPh 1,2, Def2-SVPD/SCRF=DCM, -TS, G = -5762.262426 IRC
10.14469/hpc/7797	PhICC + H-CHCl2 1,2-TS, G = -1564.354006 ΔG = 33.3 kcal/mol, IRC
10.14469/hpc/7798	PhICC + H-CHCl2 1,1-TS, G = -1564.345413, ΔG = 38.7 kcal/mol
10.14469/hpc/7799	PhICC + H-CHCl2 Reactant, G = -1564.407075
10.14469/hpc/7800	PhICC + H-CHCl2 1,1-TS, G = -1564.345413, ΔG = 38.7, IRC
10.14469/hpc/7801	PhICC + H-CHCl2 1,2-TS, G = -1564.354006, ΔG = 33.3
10.14469/hpc/7777	PhICC + CCCCIPh, branched mode to produce C5 chain, syn G = -1286.086804 IRC
10.14469/hpc/7778	PhICC + CCCCCCIPh 1,2 -TS Def2-SVPD/CPCM=DCM, G = -1362.136592 => branched mode to produce C7 chain, syn G = -1362.148139 IRC
10.14469/hpc/7592	MeI, CCSD(T)/Def2-SVPD/SCRF=DCM, G = -336.547139
10.14469/hpc/7596	Bimolecular TS C2 only wB97XD/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7899	CC + HCHCl2.
10.14469/hpc/7598	CC-IPh + PhO radical, Cs 1,2-TS Def2-TZVPPD G = -912.107781, ΔG = 21.0 kcal/mol
10.14469/hpc/7599	phenoxy radical, wB97XD/Def2-TZVPPD G = -306.778361
10.14469/hpc/7600	C-IMe + PhO radical, Nosym, 1,2-TS Def2-TZVPPD G = -720.428314
10.14469/hpc/7605	CC-IPh + PhO radical, Reactant Def2-TZVPPD G =-912.141323
10.14469/hpc/7906	Dichloromethane CCSD(T)/Def2-TZVPPD, C2v G = -958.688162
10.14469/hpc/7606	CC-IPh + 2,6-di-t-butylphenoxy, reactant, Cs, Def2-SVPD G = -1225.494635
10.14469/hpc/7607	CC-IPh + PhO radical, Cs 1,2-TS Def2-TZVPPD IPh rotated G = -912.107014 ΔG = 21.5
10.14469/hpc/7609	CC-IPh + PhO radical, Cs 1,1-TS Def2-TZVPPD G = -912.107762 ΔG =21.0
10.14469/hpc/7610	CC-IPh + 2,6-di-t-butylphenoxy, 1,2-TS, Def2-SVPD Cs symmetry G = -1225.458113 ΔG = 22.9
10.14469/hpc/7611	PhI-CC + CC-IPh, 1,1-TS, Def2-SVPD Cs symmetry, ΔG = 19.9 kcal/mol.
10.14469/hpc/7613	CC-IPh + PhO radical, Cs 1,2-TS Def2-TZVPPD IPh rotated . G = -912.107162 ΔG = 19.6
10.14469/hpc/7614	PhI-CC + CC-IPh, C2h reactant, Def2-SVPD G = -1210.058822
10.14469/hpc/7615	CC-IPh + 2,6-di-t-butylphenoxy, 1,1-TS, Def2-SVPD Cs symmetry, IPh orthog, G = -1225.454636 ΔG = 25.1 ΔΔG = 2.2
10.14469/hpc/7617	CC-IPh + 2,6-di-t-butylphenoxy, 1,1-TS, Def2-SVPD Cs symmetry G = -1225.452754, IPh coplanar
10.14469/hpc/7618	CC wB97XD/Def2-TZVPPD/CPCM=DCM G = -75.879884
10.14469/hpc/7619	PhI Def2-TZVPPD, SCRF=DCM C2v G = -529.375170
10.14469/hpc/7620	PhI-CC + CCCC-IPh, 1,1-TS, Def2-SVPD Cs symmetry G = -1286.088148 ΔG = 16.9
10.14469/hpc/7621	PhI-CC + CCCC-IPh, Cs reactant, Def2-SVPD G = -1286.115137
10.14469/hpc/7622	CC-IPh + PhO radical, 1,2-TS Def2-SVPD Cs symmetry G = -911.447928 DG = 20.0
10.14469/hpc/7623	CC-IPh + PhO radical, 1,1-TS Def2-SVPD G = -911.448953 DG = 19.4
10.14469/hpc/7624	PhI-CC Def2-TZVPPD, SCRF=DCM Cs G = -605.369213
10.14469/hpc/7625	PhI-CC + CC-IPh, 1,1-TS, Def2-SVPD Cs symmetry G = -1210.027145 ΔG = 19.9 IRC
10.14469/hpc/7627	CH3-I-CC wB97XD/Def2-TZVPPD/SCRF=DCM
10.14469/hpc/7628	CC-IPh + PhO radical, Reactant Def2-SVPD, Cs G -911.479895
10.14469/hpc/7631	CC-IPh + PhO radical, 1,2-TS Def2-SVPD Cs symmetry G = -911.447928 IRC
10.14469/hpc/7632	PhI-CC + CCCC-IPh, 1,1-TS, Def2-SVPD Cs symmetry G = -1286.088148 DG = 16.9 IRC
10.14469/hpc/7633	CC-IPh + PhO radical, 1,1-TS Def2-SVPD Cs symmetry IRC
10.14469/hpc/7641	PhICC + 9,10-dihydroanthracene, Def2-SVPD guess(mix) TS <S**2>= 0.4129 G = -1144.996296
10.14469/hpc/7644	Bimolecular MeI+ CCIMe, TS C2h CCSD(T)/Def2-SVPD/SCRF=DCM G = -748.77082
10.14469/hpc/7645	Bimolecular TS C2 only wB97XD/Def2-SVPD/SCRF=DCM -751.323261
10.14469/hpc/7648	CC-IPh + Galvinoxyl reactant, Def2-SVPD, E =-1884.0960 G = -1883.445880
10.14469/hpc/7719	Supplementary Tables S1 and S2 for Routes involving no free C2 in a DFT-computed mechanistic model for the reported room-temperature chemical synthesis of C2.
10.14469/hpc/7651	PhICC + 9,10-dihydroanthracene, Reactant G = -1145.046811
10.14469/hpc/7652	PhICC + 9,10-dihydroanthracene, Def2-SVPD guess(mix) TS IRC reverse
10.14469/hpc/7866	PhI-CC + CC-IPh, Cs monomer reactant, Def2-SVPD G = -605.030213*2 = -1,210.060426 (-1.0) -1210.058822
10.14469/hpc/7657	CC-IPh + 2,6-di-t-butylphenoxy, 1,2-TS, Def2-SVPD 2 G = -1225.458113 rotamer => G = -1225.458865
10.14469/hpc/7659	F(-) + CCIPh, wB97XD/Def2-TZVPPD, SCRF=dichloromethane, TS G = -705.346438
10.14469/hpc/7660	F(-) + CCIPh, wB97XD/Def2-SVPD, SCRF=dichloromethane Reactant G = -704.934245
10.14469/hpc/7662	F(-) + CCIPh, 1,1-TS, wB97XD/Def2-SVPD, SCRF=dichloromethane, G = -704.878130 DG = 35.2
10.14469/hpc/7664	PhICC + 9,10-dihydroanthracene, 1,2 Saddle=1, RHF G = 1145.008883
10.14469/hpc/7665	CC-IPh + 2,6-di-t-butylphenoxy, reactant, rotated, G = -1225.496559
10.14469/hpc/7666	CC-IPh + 2,6-di-t-butylphenoxy, 1,1-TS, Def2-SVPD G = -1225.457675
10.14469/hpc/7667	PhICC + 9,10-dihydroanthracene, 1,2 Saddle=1, RHF IRC forward
10.14469/hpc/7668	F(-) + CCIPh, 1,2-TS, wB97XD/Def2-SVPD, SCRF=dichloromethane, G = -704.895595 DG = 24.3
10.14469/hpc/7669	PhICC+CCCCIPh-1,2 G = -1286.077379
10.14469/hpc/7672	PhICC+CCIPh-1,2 G = -1210.034333
10.14469/hpc/7676	CC-IPh + Galvinoxyl 1,1-TS, Def2-SVPD, rotamer .G = -1883.401104
10.14469/hpc/7677	PhICC+CCIPh-1,2, Def2-SVPD, DCM, IRC
10.14469/hpc/7678	PhICC+CCCCIPh-1,2 G = -1286.079175
10.14469/hpc/7679	CC-IPh + Galvinoxyl reactant, Def2-SVPD, rotamer, G = -1883.442567 (higher energy conformer )
10.14469/hpc/7683	NH3 + CCIPh, 1,2-TS, Def2-SVPD/SCRF=DCM, G = -661.481807 IRC
10.14469/hpc/7685	CC-IPh + PhO radical, 1,2-TS Def2-SVPD Cs symmetry G = -911.447928 gas phase
10.14469/hpc/7686	CC-IPh + PhO radical, 1,1-TS Def2-SVPD G = -911.448953 gas phase

Associated DOIs

Current dataset ...	DOI	Description
References	10.1039/D1CP02056K	Routes involving no free C2 in a DFT-computed mechanistic model for the reported room-temperature chemical synthesis of C2.
References	10.26434/chemrxiv.13560260	ChemRxiv preprint

Edit