Fluorine-Centered Halogen Bonding: A Factor in Recognition Phenomena and Reactivity
Source abstract
Abstract
Because of the anisotropies of their electronic charge distributions, many covalently bound halogen atoms have regions of positive electrostatic potential (positive σ-holes) on their outer portions. Through these, the halogens can interact attractively with negative sites. It has sometimes been questioned whether fluorine, the least polarizable halogen, can form halogen bonds, especially in solids. Here we present computational and crystallographic evidence demonstrating that it can indeed do so, in both the gaseous and the solid phases. We show computationally, through a series of examples, that fluorine can have positive σ-holes when linked to strongly electron-withdrawing residues and that it can interact with Lewis bases to form gas phase halogen-bonded complexes. Through statistical analyses of data from the Cambridge Structural Database, we demonstrate that such fluorines do also halogen bond in the solid state, and we show several specific cases of this.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Crystallography and molecular interactions · Inorganic Fluorides and Related Compounds · Ionic liquids properties and applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
NFMLab, Department of Chemistry, Materials and Chemical Engineering, “Giulio Natta”, Politecnico di Milano, Via L. Mancinelli 7, 20131 Milan, Italy
CNST-IIT@POLIMI, Via Pascoli 70/3, 20133 Milan, Italy
CleveTheoComp, 1951 W. 26th Street, Suite 409, Cleveland, Ohio 44113, United States
References (77)
Show source-provided references
1. Stevens E. D. · Mol. Phys. · 1979 · 37 · 2710.1080/00268977900100041 ↗
2. Nyburg S. C. · Proc. R. Soc. London A · 1979 · 367 · 2910.1098/rspa.1979.0074 ↗
3. Ikuta S. · J. Mol. Struct. (Theochem) · 1990 · 205 · 19110.1016/0166-1280(90)85119-8 ↗
4. Pedireddi V. R. · J. Chem. Soc., Perkin Trans. 2 · 1994 · 235310.1039/p29940002353 ↗
5. Price S. L. · J. Am. Chem. Soc. · 1994 · 116 · 491010.1021/ja00090a041 ↗
6. Tsirelson V. G. · Acta Crystallogr. · 1995 · 51 · 14310.1107/S0108767394009463 ↗
7. Lommerse J. P. M. · J. Am. Chem. Soc. · 1996 · 118 · 310810.1021/ja953281x ↗
8. Torii H. · J. Chem. Phys. · 2003 · 119 · 219210.1063/1.1585016 ↗
9. Grabowski S. J. · Chem. Phys. Lett. · 2006 · 427 · 5110.1016/j.cplett.2006.06.060 ↗
10. Clark T. · J. Mol. Model. · 2007 · 13 · 29110.1007/s00894-006-0130-2 ↗
11. Politzer P. · J. Mol. Model. · 2007 · 13 · 64310.1007/s00894-007-0176-9 ↗
12. Politzer P. · Int. J. Quantum Chem. · 2007 · 107 · 304610.1002/qua.21419 ↗
13. Riley K. E. · J. Chem. Theor. Comput. · 2009 · 5 · 15510.1021/ct8004134 ↗
14. Politzer P. · Phys. Chem. Chem. Phys. · 2010 · 12 · 774810.1039/c004189k ↗
15. 10.1007/s00894-011-1015-610.1007/s00894-011-1015-6 ↗
16. Auffinger P. · Proc. Nat. Acad. Sci. U. S. A. · 2004 · 101 · 1678910.1073/pnas.0407607101 ↗
17. Metrangolo P. · Acc. Chem. Res. · 2005 · 38 · 38610.1021/ar0400995 ↗
18. Politzer P. · J. Mol. Model. · 2007 · 13 · 30510.1007/s00894-006-0154-7 ↗
19. Murray J. S. · Aust. J. Chem. · 2010 · 63 · 159810.1071/CH10259 ↗
20. Di Paolo T. · Chem. Phys. Lett. · 1974 · 26 · 46610.1016/0009-2614(74)80392-1 ↗
21. Di Paolo T. · Can. J. Chem. · 1974 · 52 · 361210.1139/v74-540 ↗
22. Corradi E. · Angew. Chem., Int. Ed. · 2000 · 39 · 178210.1002/(SICI)1521-3773(20000515)39:10<1782::AID-ANIE1782>3.0.CO;2-5 ↗
23. Alkorta I. · J. Phys. Chem. A · 2008 · 112 · 1085610.1021/jp806101t ↗
24. Shields Z. · Int. J. Quantum Chem. · 2010 · 110 · 282310.1002/qua.22787 ↗
25. Valerio G. · J. Phys. Chem. A · 2000 · 104 · 161710.1021/jp993415j ↗
26. Riley K. E. · J. Chem. Theor. Comput. · 2008 · 4 · 23210.1021/ct700216w ↗
27. Murray-Rust P. · J. Am. Chem. Soc. · 1979 · 101 · 437410.1021/ja00509a056 ↗
28. Murray-Rust P. · J. Am. Chem. Soc. · 1983 · 105 · 320610.1021/ja00348a041 ↗
29. Ramasubbu N. · J. Am. Chem. Soc. · 1986 · 108 · 430810.1021/ja00275a012 ↗
30. Chopra D. · Cryst. Growth Des. · 2007 · 7 · 86810.1021/cg0604881 ↗
31. Politzer P. · J. Mol. Model. · 2008 · 14 · 65910.1007/s00894-008-0280-5 ↗
32. Voth A. R. · Proc. Nat. Acad. Sci. · 2007 · 104 · 618810.1073/pnas.0610531104 ↗
33. Metrangolo P. · J. Polym. Sci. A · 2007 · 45 · 110.1002/pola.21725 ↗
34. Lu Y.-X. · Chem. Phys. Lett. · 2007 · 449 · 610.1016/j.cplett.2007.09.087 ↗
35. Metrangolo, P.; Resnati, G.; Pilati, T.; Biella, S.InHalogen Bonding: Fundamentals and Applications;Metrangolo, P.; Resnati, G., Eds.Springer:Berlin, 2008; pp105–136.10.1007/978-3-540-74330-9 ↗
36. Rissanen K. · CrystEngComm · 2008 · 10 · 110710.1039/b803329n ↗
37. Legon A. C. · Angew. Chem., Int. Ed. · 1999 · 38 · 268610.1002/(SICI)1521-3773(19990917)38:18<2686::AID-ANIE2686>3.0.CO;2-6 ↗
38. Chopra D. · CrystEngComm · 2011 · 13 · 217510.1039/c0ce00538j ↗
39. 10.1039/c1ce05554b10.1039/c1ce05554b ↗
40. Politzer, P.; Murray, J. S.InPractical Aspects of Computational Chemistry;Leszczynski, J.; Shukla, M. K., Eds.Springer:Amsterdam, 2009; pp149–167.
41. Exner O. · J. Phys. Org. Chem. · 2006 · 19 · 39310.1002/poc.1093 ↗
42. Barton D. H. R. · Chem. Commun. · 1968 · 804
43. Barton D. H. R · Chem. Commun. · 1969 · 22710.1039/c29690000227 ↗
44. Rozen S. · Chem. Rev. · 1996 · 96 · 171710.1021/cr941147+ ↗
45. Taylor S. D. · Tetradedron · 1999 · 55 · 1243110.1016/S0040-4020(99)00748-6 ↗
46. Burdeniuc J. · J. Fluorine Chem. · 1998 · 91 · 4910.1016/S0022-1139(98)00215-2 ↗
47. Hamor T. A. · J. Chem. Soc., Perkin Trans. 2 · 1974 · 14010.1039/p29740000140 ↗
48. Polyakov O. G. · Organometallics · 1999 · 18 · 376910.1021/om990196f ↗
49. Deck P. A. · J. Organomet. Chem. · 2006 · 691 · 197310.1016/j.jorganchem.2005.12.056 ↗
50. Takahashi A. · Chem. Commun. · 2008 · 238510.1039/b800815a ↗
51. Stewart R. F. · Chem. Phys. Lett. · 1979 · 65 · 33510.1016/0009-2614(79)87077-3 ↗
52. Politzer P. · 198110.1007/978-1-4757-9634-6 ↗
53. Politzer P. · Theor. Chem. Acc. · 2002 · 108 · 13410.1007/s00214-002-0363-9 ↗
54. Murray J. S. · Wiley Interdisc. Rev., Comp. Mol. Sci. · 2011 · 1 · 15310.1002/wcms.19 ↗
55. Bader R. F. W. · J. Am. Chem. Soc. · 1987 · 109 · 796810.1021/ja00260a006 ↗
56. Zhao Y. · Theor. Chem. Acc. · 2008 · 120 · 21510.1007/s00214-007-0310-x ↗
57. Gaussian 09, Revision A.1;Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J.Gaussian, Inc.:Wallingford, CT, 2009.
58. Bulat F. A. · J. Mol. Model. · 2010 · 16 · 167910.1007/s00894-010-0692-x ↗
59. Grimme S. · J. Comput. Chem. · 2006 · 27 · 178710.1002/jcc.20495 ↗
60. 10.1007/s00894-011-1089-110.1007/s00894-011-1089-1 ↗
61. Wozniak K. · J. Phys. Chem. · 1994 · 98 · 1375510.1021/j100102a049 ↗
62. Göbel M. · Nat. Chem. · 2009 · 1 · 22910.1038/nchem.179 ↗
63. Murray J. S. · J. Chem. Phys. · 2009 · 130 · 104304(1–6)10.1063/1.3082406 ↗
64. Macaveiu L. · Struct. Chem. · 2010 · 21 · 13910.1007/s11224-009-9550-9 ↗
65. Bondi A. · J. Phys. Chem. · 1964 · 68 · 44110.1021/j100785a001 ↗
66. Della Védova C. O. · Inorg. Chem. · 2004 · 43 · 406410.1021/ic049865u ↗
67. Hathwar V. R. · Cryst. Growth Des. · 2011 · 11 · 133810.1021/cg1015862 ↗
68. Katritzky A. R. · New J. Chem. · 2006 · 30 · 34910.1039/b509260d ↗
69. Bittner J. · Chem. Ber. · 1991 · 124 · 8710.1002/cber.19911240114 ↗
70. Takahashi A. · Chem. Commun. · 2008 · 238510.1039/b800815a ↗
71. Atovmyan L. O. · Izv. Akad. Nauk SSSR, Ser. Khim. (Russ.) (Russ. Chem. Bull.) · 1984 · 33 · 543
72. Lentz D. · J. Organomet. Chem. · 2002 · 641 · 21510.1016/S0022-328X(01)01297-9 ↗
73. Hamor T. A. · J. Chem. Soc., Perkin Trans. 2 · 1974 · 14010.1039/p29740000140 ↗
74. Polyakov O. G. · Organometallics · 1999 · 18 · 376910.1021/om990196f ↗
75. Nockemann P. · Inorg. Chem. · 2008 · 47 · 998710.1021/ic801213z ↗
76. Nockemann P. · J. Phys. Chem. B · 2006 · 110 · 2097810.1021/jp0642995 ↗
77. Platonov V. E. · J. Fluorine Chem. · 2001 · 109 · 13110.1016/S0022-1139(01)00367-0 ↗