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FAIR Data table.c Bromination of benzene
SystemaΔΔG298DOIbIRC AnimationIRC, DOIb
Separated Benzene + nBr2 0.0(0.0)d189806, 189804
191250,d191249d		--
1Br2
Benzene + 1Br2 1.8 (3.2)d189499, 189580--
SEAr reaction, Cs symmetry, 2 -ve force constants 46.0 (50.9)d189612, 189704IRC189707
SEAr reaction, C1 symmetry, 1 -ve force constants 44.3 (47.3)e189495, 189638IRC189503
SEAr reaction, Cs symmetry, 2 -ve force constants, biradical 39.7189621--
SEAr reaction, C1 symmetry, 1 -ve force constants, biradical 38.6189517IRC29x, 29y
AdE, cis-1,2-addition 42.9(47.5)d189500, 189555IRC189502
AdE, cis-1,2-addition, biradical 37.9191199IRC191200,191201
cis-1,2-dibromocyclohexadiene 19.3191202NBOf,NBOg-
trans-di-axial-1,2-dibromocyclohexadiene 14.0(12.4)189526, 189706--
trans-di-equatorial-1,2-dibromocyclohexadiene 22.0189529--
Bromobenzene + HBr -9.9 (-11.9)d 189535, 189711--
Separated Bromobenzene + HBr -12.7 (-15.0)d 191252, 191253
191254,d 195500d		--
2Br2
Benzene + 2Br2 4.6 (5.0)d189501, 189616--
Benzene + 2Br2 allotrope 27.4 (30.2)189554, 189703--
SEAr reaction, Cs symmetry, 2 -ve force constants 33.8 (37.1)d189498, 189598 IRC189519
AdE, trans-1,2-addition 31.8 189496IRC189506
AdE, cis-1,4-addition 31.4 189497IRC189504
AdE, trans-1,4-addition, 1st C-Br 29.3 189516IRC189531
AdE, trans-1,4-addition, Wheland intermediate 23.7189524--
AdE, trans-1,4-addition, 2nd C-Br 30.5189515IRC189530
trans-1,4-dibrobromocyclohexadiene+Br2 17.2 189537--
cis-1,4-dibrobromocyclohexadiene+Br2 19.4 189544--
trans-1,2-dibrobromocyclohexadiene+Br2 16.3189538--
Bromobenzene+HBr+1Br2 -5.5 (-7.6)d191242, 190787--
Separated Bromobenzene + HBr + Br2 -12.7 (-15.0)d 191252, 191253
191254,d 195500d		--
3Br2
Benzene + 3Br2 7.8189505--
Benzene + 3Br2 isomer 9.6189548--
SEAr concerted substitution, Cs, 2-ve FC 30.1191206IRC189568
SEAr concerted substitution, C1, 1-ve FC 26.6191256IRC191257
AdE, trans-1,2-addition 26.2191204IRC189547
SEAr stepwise substitution, C-Br bond formation 28.7191224IRC191232
SEAr stepwise substitution, Wheland intermediate 17.6191230--
SEAr stepwise substitution, proton removal 21.9189581IRC189609
trans-1,2-dibrobromocyclohexadiene+2Br2 20.3189528--
Bromobenzene+HBr+2Br2 -1.2 189599--
Separated Bromobenzene + HBr + 2Br2 -12.7 (-15.0)d 191252, 191253
191254,d 195500d		--
4Br2
Benzene + 4Br2 12.2189750--
SEAr concerted substitution, Cs, 1-ve FC 36.5 189722IRC189769,189770
SEAr concerted substitution, Cs, 1-ve FC 26.5191241IRC
NCI 		191247
Bromobenzene + HBr + 3Br2 2.0 189771--
Separated Bromobenzene + HBr + 3Br2 -12.7 (-15.0)d 191252, 191253
191254,d 195500d		--
5Br2
Benzene + 5Br2 15.7189768--
Crystal structure, PEVTER -10.5517/CCZF3K1-10.1002/anie.201209928
Crystal structure, ODAQER -10.5517/CCX1QN9-10.1002/anie.201105237
SEAr concerted substitution, Cs, 2-ve FC 35.6 189705IRC189765
SEAr stepwise substitution, C-Br formation 32.0191237IRC
NCI 		191244, 191243
TSEAr stepwise substitution, Wheland intermediate 21.3191238-
TSEAr stepwise substitution, proton removal 22.2191236IRC191244,191243
Bromobenzene + HBr + 4Br2 7.0189767--
Separated Bromobenzene + HBr + 4Br2 -12.7 (-15.0)d 191252, 191253
191254,d 195500d		--
aClick on any energy to load a 3D-coordinate for a B3LYP+D3/6-311++G(2d,2p)/SCRF=benzene model. Relative free energies in kcal/mol, for a standard state of 0.041M. bA digital repository identifier (DOI), resolved as e.g. http://doi.org/10.14469/ch/189499 cThis FAIR datatable is assigned the persistent identifier doi:10.6084/m9.figshare.1299202 as recommended in the Joint Declaration of Data Citation Principles dAt the B2PLYPD3/6-311++D(2d,2p)/SCRF=benzene level. eIdentical to TS_1 (cis-addition). fNatural bond orbitals illustrating the interaction between the highest π-C=C occupied NBO and the axial C-Br-σ* lowest vacant NBO. gNatural bond orbitals illustrating the smaller interaction between the lower π-C=C occupied NBO and the equatorial C-Br-σ* vacant NBO. hAll attempts to locate this transition state led to direct 1,2-trans-addition instead.