The Mechanism and Design of Asymmetric Co-Arctate Br+ (Mobius) Atom Transfers Between Alkenes. A Computational Study
DOI: 10.14469/hpc/13929 Metadata
Created: 2024-03-20 07:40
Last modified: 2024-03-20 11:00
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Co-author: D. Christopher Braddock
Description
Ab initio calculations at the correlated MP2 and B3LYP/pVTZ level reveal that a bromine cation transfer between two alkenes involves a symmetrically 4-coordinated species which is an energy minimum in the gas phase energy profile. Electron withdrawing and donating substituents on one alkene distort the position of the bromine respectively away from and towards the substituted alkene. Alkenes strained by incorporating a trans configuration into 6-8 membered rings preferentially bind the Br cation, an equilibrium which can be tuned by using a combination of substituents and strain. The classification of such an atom transfer as a concerted coarctate reaction is discussed. Original publication: Internet Journal of Chemistry [online computer file] Volume: 4 Pages: No pp. given, Article No. 10 Journal 2001
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| metohib3lyp631Ggs2.mol | 1KB | chemical/x-mdl-molfile | Data Files |
| ciclo8gs2b3lyp.mol | 2KB | chemical/x-mdl-molfile | Data Files |
| ciclooctdicf3dicf3gs2pb3lyp.mol | 3KB | chemical/x-mdl-molfile | Data Files |
| cyanob3lyp631Ggs2.mol | 1KB | chemical/x-mdl-molfile | Data Files |
| cyclooctdicf3gs2.mol | 3KB | chemical/x-mdl-molfile | Data Files |
| cyclooctdicf3gs2pb3lyp.mol | 3KB | chemical/x-mdl-molfile | Data Files |
| 6-1.mol | 1KB | chemical/x-mdl-molfile | Data Files |
| 6-2.mol | 2KB | chemical/x-mdl-molfile | Data Files |
| 8-1-cf3.mol | 2KB | chemical/x-mdl-molfile | Data Files |
| 8-1.mol | 2KB | chemical/x-mdl-molfile | Data Files |
| 8-2-cf3.mol | 4KB | chemical/x-mdl-molfile | Data Files |
| 8-2.mol | 3KB | chemical/x-mdl-molfile | Data Files |
| freqdefcyoctenedicf3tsb3lyp.xyz | 80KB | chemical/x-xyz | Data Files |
| mp2-h.xyz | 12KB | chemical/x-xyz | Data Files |
| mp2-sp-h1.xyz | 13KB | chemical/x-xyz | Data Files |
| mp2-sp-h2.xyz | 12KB | chemical/x-xyz | Data Files |
| frecuencia.xyz | 80KB | chemical/x-xyz | Data Files |
| frecuencia2.xyz | 80KB | chemical/x-xyz | Data Files |
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| methoxigs1.PDB | 2KB | application/octet-stream | Data Files |
| methoxigs1p.PDB | 2KB | application/octet-stream | Data Files |
| methoxigs2.PDB | 2KB | application/octet-stream | Data Files |
| methoxigs2p.PDB | 2KB | application/octet-stream | Data Files |
| methoxits.PDB | 2KB | application/octet-stream | Data Files |
| ciclpo6gs1.PDB | 3KB | application/octet-stream | Data Files |
| cyanob3lyp3-21Ggs2.PDB | 1KB | application/octet-stream | Data Files |
| cyanogs1.PDB | 1KB | application/octet-stream | Data Files |
| cyanogs1p.PDB | 1KB | application/octet-stream | Data Files |
| cyanogs2.PDB | 1KB | application/octet-stream | Data Files |
| cyanogs2p.PDB | 1KB | application/octet-stream | Data Files |
| cyanots.PDB | 1KB | application/octet-stream | Data Files |
| cyclooctdicf3gs1.PDB | 4KB | application/octet-stream | Data Files |
| cyclooctdicf3gs1p.PDB | 4KB | application/octet-stream | Data Files |
| cyclooctdicf3gs2p.PDB | 4KB | application/octet-stream | Data Files |
| cyclooctdicf3tsb3lyp.PDB | 4KB | application/octet-stream | Data Files |
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| cyclooctdicf3tsb3lyp631G.PDB | 4KB | application/octet-stream | Data Files |
| 2-gs-b3.pdb | 1KB | chemical/x-pdb | Data files |
| 2-gs-b6.pdb | 1KB | chemical/x-pdb | Data files |
| 2-gs-bTZ.pdb | 1KB | chemical/x-pdb | Data files |
| 2-gs-mp6.mol | 1KB | chemical/x-mdl-molfile | Data files |
| 2-gs-mp6.pdb | 1KB | chemical/x-pdb | Data files |
| 2-gs-rh3.pdb | 1KB | chemical/x-pdb | Data files |
| 2-gs-rh6.pdb | 1KB | chemical/x-pdb | Data files |
| 2-gs-rh6p.pdb | 1KB | chemical/x-pdb | Data files |
| 2-gs-rhTZ.pdb | 1KB | chemical/x-pdb | Data files |
| 3-ts-b6.pdb | 1KB | chemical/x-pdb | Data files |
| 3-ts-bTZ.pdb | 1KB | chemical/x-pdb | Data files |
| 3-ts-rh3.pdb | 1KB | chemical/x-pdb | Data files |
| 3-ts-rh6.pdb | 1KB | chemical/x-pdb | Data files |
| 3-ts-rh6p.pdb | 1KB | chemical/x-pdb | Data files |
| 3-ts-rhTZ.pdb | 1KB | chemical/x-pdb | Data files |
| 4-ts-b3.pdb | 1KB | chemical/x-pdb | Data files |
| 4-ts-bTZ.pdb | 1KB | chemical/x-pdb | Data files |
| ciclo6gs1.PDB | 3KB | application/octet-stream | Data files |
| ciclo6gs2.PDB | 3KB | application/octet-stream | Data files |
| ciclo7b3lypgs2.PDB | 3KB | application/octet-stream | Data files |
| 3-ts-mp6.xyz | 12KB | chemical/x-xyz | Data files |
| Br+_figure.gif | 5KB | image/gif | Structure |
| 4-6.gif | 2KB | image/gif | Diagrams |
| figure1.gif | 2KB | image/gif | Diagrams |
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| ciclo7gs1.PDB | 3KB | application/octet-stream | Data files |
| ciclo7gs2.PDB | 3KB | application/octet-stream | Data files |
| ciclo8gs1.PDB | 3KB | application/octet-stream | Data files |
| ciclo8gs2.PDB | 3KB | application/octet-stream | Data files |
| ciclo6b3lypgs2.PDB | 3KB | application/octet-stream | Data files |
| scheme3.html | 327 | text/html | HTML files |
| scheme2.html | 329 | text/html | HTML files |
| scheme1.html | 328 | text/html | HTML files |
| 4-6.html | 317 | text/html | HTML files |
| link-mp2-h.html | 1KB | text/html | HTML Files |
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| index.html | 38KB | text/html | Root document, V1 |
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| index.html | 40KB | text/html | Root document, V3 |
Associated DOIs
| Current dataset ... | DOI | Description |
|---|---|---|
| References | 10.14469/hpc/13930 | Data for 3D model |
| References | 10.14469/hpc/13931 | Data for 3D model |
| References | 10.14469/hpc/13932 | Data for 3D model |
Subject Keywords
| Keyword | Value |
|---|---|
| inchi | InChI=1S/C4H9Br/c1-2-5(1)6-3-4-7-5/h3-5H,1-2H2 |
| inchi | InChI=1S/C3H7BO.C2H4/c1-5-3-2-4-3;1-2/h3-4H,2H2,1H3;1-2H2/t3-;/m0./s1 |
| inchi | InChI=1S/C4H8B/c1-2-5(1)3-4-5/h1-4H2 |
| inchi | InChI=1S/C3H6O.C2H4.BH3/c1-3-4-2;1-2;/h3H,1H2,2H3;1-2H2;1H3 |
| inchi | InChI=1S/C2H5B.C2H4/c1-2-3-1;1-2/h3H,1-2H2;1-2H2 |
| inchi | InChI=1S/C6H11B.C2H4/c1-2-4-6-5(3-1)7-6;1-2/h5-7H,1-4H2;1-2H2/t5-,6-;/m0./s1 |
| inchi | InChI=1S/C4H8B/c1-2-5(1)3-4-5/h1-4H2 |
| inchi | InChI=1S/C3H3N.C2H4.BH3/c1-2-3-4;1-2;/h2H,1H2;1-2H2;1H3 |
| inchi | InChI=1S/C4H8B/c1-2-5(1)3-4-5/h1-4H2 |
| inchi | InChI=1S/C3H3N.C2H5B/c1-2-3-4;1-2-3-1/h2H,1H2;3H,1-2H2 |
| inchi | InChI=1S/C3H3BrN.C2H4/c4-2-1-3-5;1-2/h1H,2H2;1-2H2 |
| inchi | InChI=1S/C10H14F6.C2H6.BrH/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2;/h7-8H,1-6H2;1-2H3;1H/t7-,8-;;/m1../s1 |
| inchi | InChI=1S/C3H6O.C2H4Br/c1-3-4-2;1-2-3/h3H,1H2,2H3;1-2H2 |
| inchi | InChI=1S/C20H25BrF12/c22-17(23,24)13-9-5-1-2-6-10-14(13,18(25,26)27)21(13)15(19(28,29)30)11-7-3-4-8-12-16(15,21)20(31,32)33-34-12/h12,21H,1-11H2/t12-,13+,14+,15+,16+/m1/s1 |
| inchi | InChI=1S/C10H12F6.C2H4.Br/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2;/h1-6H2;1-2H2;/b8-7+;; |
| inchi | InChI=1S/C8H16.C2H6.BrH/c1-2-4-6-8-7-5-3-1;1-2;/h1-8H2;1-2H3;1H |
| inchi | InChI=1S/C10H13BF6.C2H4/c12-9(13,14)7-5-3-1-2-4-6-8(7,11-7)10(15,16)17;1-2/h11H,1-6H2;1-2H2/t7-,8-;/m0./s1 |
| inchi | InChI=1S/C10H14F6.C2H4.BH3/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2;/h7-8H,1-6H2;1-2H2;1H3/t7-,8-;;/m1../s1 |
| inchi | InChI=1S/C3H6O.C2H5B/c1-3-4-2;1-2-3-1/h3H,1H2,2H3;3H,1-2H2 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C3H6O.C2H5B/c1-3-4-2;1-2-3-1/h3H,1H2,2H3;3H,1-2H2 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C3H7BO.C2H4/c1-5-3-2-4-3;1-2/h3-4H,2H2,1H3;1-2H2/t3-;/m1./s1 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C3H6O.C2H4.BH3/c1-3-4-2;1-2;/h3H,1H2,2H3;1-2H2;1H3 |
| inchi | InChI=1S/C2H5B.C2H4/c1-2-3-1;1-2/h3H,1-2H2;1-2H2 |
| inchi | InChI=1S/C3H9BO.C2H4/c1-5-3-2-4;1-2/h2-4H2,1H3;1-2H2 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C3H3N.C2H5B/c1-2-3-4;1-2-3-1/h2H,1H2;3H,1-2H2 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C3H4BN.C2H4/c5-2-3-1-4-3;1-2/h3-4H,1H2;1-2H2/t3-;/m1./s1 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C3H3N.C2H4.BH3/c1-2-3-4;1-2;/h2H,1H2;1-2H2;1H3 |
| inchi | InChI=1S/C4H8B/c1-2-5(1)3-4-5/h1-4H2 |
| inchi | InChI=1S/C10H14F6.C2H5B/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2-3-1/h7-8H,1-6H2;3H,1-2H2/t7-,8-;/m1./s1 |
| inchi | InChI=1S/C4H8B/c1-2-5(1)3-4-5/h1-4H2 |
| inchi | InChI=1S/C10H14F6.C2H5Br/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2-3-1/h7-8H,1-6H2;3H,1-2H2/t7-,8-;/m1./s1 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C16H29Br/c1-2-6-10-14-13(9-5-1)17(14)15-11-7-3-4-8-12-16(15)17/h13-17H,1-12H2/t13-,14-,15-,16-/m0/s1 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C10H14F6.C2H6.BrH/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2;/h7-8H,1-6H2;1-2H3;1H/t7-,8-;;/m1../s1 |
| inchi | InChI=1S/2C2H4.BH3/c2*1-2;/h2*1-2H2;1H3 |
| inchi | InChI=1S/C8H16Br/c1-2-4-8-7(3-1)9(8)5-6-9/h7,9H,1-6,8H2/t7-/m1/s1 |
| inchi | InChI=1S/C6H11B.C2H4/c1-2-4-6-5(3-1)7-6;1-2/h5-7H,1-4H2;1-2H2/t5-,6-;/m0./s1 |
| inchi | InChI=1S/C10H12F6.C2H4Br/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2-3/h1-6H2;1-2H2/b8-7+; |
| inchi | InChI=1S/C8H15B/c1-2-4-8-7(3-1)9(8)5-6-9/h7H,1-6,8H2/t7-/m1/s1 |
| inchi | InChI=1S/C3H9N.C2H6.BrH/c1-2-3-4;1-2;/h2-4H2,1H3;1-2H3;1H |
| inchi | InChI=1S/C7H13B.C2H4/c1-2-4-6-7(8-6)5-3-1;1-2/h6-8H,1-5H2;1-2H2/t6-,7-;/m0./s1 |
| inchi | InChI=1S/C3H4BN.C2H4/c5-2-3-1-4-3;1-2/h3-4H,1H2;1-2H2/t3-;/m0./s1 |
| inchi | InChI=1S/C12H21Br/c1-2-6-10-9(5-1)13(10)11-7-3-4-8-12(11)13/h9-13H,1-8H2/t9-,10-,11-,12-/m0/s1 |
| inchi | InChI=1S/C2H4Br.C2H4/c1-2-3;1-2/h1-2H2;1-2H2 |
| inchi | InChI=1S/C3H7BrO.C2H6/c1-5-3-2-4;1-2/h2-3H2,1H3;1-2H3 |
| inchi | InChI=1S/C7H13B.C2H4/c1-2-4-6-7(8-6)5-3-1;1-2/h6-8H,1-5H2;1-2H2/t6-,7-;/m0./s1 |
| inchi | InChI=1S/2C2H4.Br/c2*1-2;/h2*1-2H2; |
| inchi | InChI=1S/C9H16B/c1-2-4-8-9(5-3-1)10(8)6-7-10/h8-9H,1-7H2/t8-,9-/m0/s1 |
| inchi | InChI=1S/C2H4Br.C2H4/c1-2-3;1-2/h1-2H2;1-2H2 |
| inchi | InChI=1S/C10H12F6.C2H4.Br/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2;/h1-6H2;1-2H2;/b8-7+;; |
| inchi | InChI=1S/C8H15B.C2H4/c1-2-4-6-8-7(9-8)5-3-1;1-2/h7-9H,1-6H2;1-2H2/t7-,8-;/m0./s1 |
| inchi | InChI=1S/C10H14F6.C2H5Br/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2-3-1/h7-8H,1-6H2;3H,1-2H2/t7-,8-;/m1./s1 |
| inchi | InChI=1S/C10H18B/c1-2-4-6-10-9(5-3-1)11(10)7-8-11/h9-10H,1-8H2/t9-,10-/m0/s1 |
| inchi | InChI=1S/C12H17BrF6/c14-11(15,16)9-5-3-1-2-4-6-10(9,12(17,18)19)13(9)7-8-13/h13H,1-8H2/t9-,10-/m0/s1 |
| inchi | InChI=1S/C10H19Br/c1-2-4-6-10-9(5-3-1)11(10)7-8-11/h9-11H,1-8H2/t9-,10-/m0/s1 |
| inchi | InChI=1S/C6H11B.C2H4/c1-2-4-6-5(3-1)7-6;1-2/h5-7H,1-4H2;1-2H2/t5-,6-;/m0./s1 |
| inchi | InChI=1S/C10H12F6.C2H4.Br/c11-9(12,13)7-5-3-1-2-4-6-8(7)10(14,15)16;1-2;/h1-6H2;1-2H2;/b8-7+;; |
| inchikey | UGIUZJJYTJJTRE-GEMLJDPKSA-N |
| inchikey | HALXKSRPHVNTCA-UWVGGRQHSA-N |
| inchikey | YTAWXCBNXRVBPI-IUCAKERBSA-N |
| inchikey | MNXBJBUIUBOKEW-UHFFFAOYSA-N |
| inchikey | RQRZEOCDBTXCFW-LEUCUCNGSA-N |
| inchikey | SPWIOBOJLHUGNT-UHFFFAOYSA-N |
| inchikey | CAQYUHXQPXDBKC-UHFFFAOYSA-N |
| inchikey | RMDJPCFPBVTXLC-MIIBGCIDSA-N |
| inchikey | UORXITIMQBJADC-UHFFFAOYSA-N |
| inchikey | RMDJPCFPBVTXLC-MIIBGCIDSA-N |
| inchikey | UORXITIMQBJADC-UHFFFAOYSA-N |
| inchikey | QQXFLDQTGLGBSG-UHFFFAOYSA-N |
| inchikey | UYWKLPIWGVXEFK-AENDTGMFSA-N |
| inchikey | UHAFPJJNFKSCJG-UHFFFAOYSA-N |
| inchikey | GFEALKWFKMSIOR-UHFFFAOYSA-N |
| inchikey | GSVQYUNFRVLWFA-RHJRFJOKSA-N |
| inchikey | UYWKLPIWGVXEFK-DFWYDOINSA-N |
| inchikey | PJBBMDIAZBAAAG-WSZWBAFRSA-N |
| inchikey | GFEALKWFKMSIOR-UHFFFAOYSA-N |
| inchikey | GSVQYUNFRVLWFA-RHJRFJOKSA-N |
| inchikey | UGIUZJJYTJJTRE-GEMLJDPKSA-N |
| inchikey | PJBBMDIAZBAAAG-WSZWBAFRSA-N |
| inchikey | JHUSJUHSFMDNIA-UHFFFAOYSA-N |
| inchikey | GSVQYUNFRVLWFA-RHJRFJOKSA-N |
| inchikey | LXXWCTQXTOJYRM-UHFFFAOYSA-N |
| inchikey | RMDJPCFPBVTXLC-MIIBGCIDSA-N |
| inchikey | WZOXLDHIMBVKAA-DFWYDOINSA-N |
| inchikey | NYMCSAWHHVYROP-VGWMRTNUSA-N |
| inchikey | LXXWCTQXTOJYRM-UHFFFAOYSA-N |
| inchikey | QXNDDADIVYIKFV-RHJRFJOKSA-N |
| inchikey | WZOXLDHIMBVKAA-AENDTGMFSA-N |
| inchikey | SALFEGFONLISIM-UHFFFAOYSA-N |
| inchikey | JHUSJUHSFMDNIA-UHFFFAOYSA-N |
| inchikey | BCHQPGVEEYWUBG-UHFFFAOYSA-N |
| inchikey | OPGZBYFTGQIFTP-SCLLHFNJSA-N |
| inchikey | QXNDDADIVYIKFV-RHJRFJOKSA-N |
| inchikey | APMPCSRXMHOJHA-UHFFFAOYSA-N |
| inchikey | HKWOPZGIGLZVIT-SCLLHFNJSA-N |
| inchikey | ZPIYKXJVYVEDBF-SSDOTTSWSA-N |
| inchikey | WXTZVOJMLXQPFB-BJDJZHNGSA-N |
| inchikey | VYNNDHDQFQASPC-UWVGGRQHSA-N |
| inchikey | FNISTMAWHIDHKW-UWVGGRQHSA-N |
| inchikey | WTPPLDJUVPGUBS-YXMSTPNBSA-N |
| inchikey | XAFSRJITPCKSCV-USRGLUTNSA-N |
| inchikey | MNXBJBUIUBOKEW-UHFFFAOYSA-N |
| inchikey | GKKQDGDPBSBFSY-UHFFFAOYSA-N |
| inchikey | JRNHUUVFMQNHDP-UHFFFAOYSA-N |
| inchikey | URUOBZDBLGECBI-UHFFFAOYSA-N |
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