Charge-Shift Bonding: A New and Unique Form of Bonding.
bond theory
charge-shift bonds
covalent bonds
ionic bonds
valence bonds
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
13 Jan 2020
13 Jan 2020
Historique:
received:
08
08
2019
pubmed:
3
9
2019
medline:
3
9
2019
entrez:
3
9
2019
Statut:
ppublish
Résumé
Charge-shift bonds (CSBs) constitute a new class of bonds different than covalent/polar-covalent and ionic bonds. Bonding in CSBs does not arise from either the covalent or the ionic structures of the bond, but rather from the resonance interaction between the structures. This Essay describes the reasons why the CSB family was overlooked by valence-bond pioneers and then demonstrates that the unique status of CSBs is not theory-dependent. Thus, valence bond (VB), molecular orbital (MO), and energy decomposition analysis (EDA), as well as a variety of electron density theories all show the distinction of CSBs vis-à-vis covalent and ionic bonds. Furthermore, the covalent-ionic resonance energy can be quantified from experiment, and hence has the same essential status as resonance energies of organic molecules, e.g., benzene. The Essay ends by arguing that CSBs are a distinct family of bonding, with a potential to bring about a Renaissance in the mental map of the chemical bond, and to contribute to productive chemical diversity.
Identifiants
pubmed: 31476104
doi: 10.1002/anie.201910085
doi:
Types de publication
Journal Article
Review
Langues
eng
Sous-ensembles de citation
IM
Pagination
984-1001Subventions
Organisme : Israel Science Foundation
ID : 520/18
Informations de copyright
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Références
S. Shaik, J. Comput. Chem. 2007, 28, 51.
B. Bensaude-Vincent, I. Stengers, A History of Chemistry, English translation (Ed.: D. van Dam), Harvard University Press, Cambridge, 1996, p. 74.
W. H. Brock, The Norton History of Chemistry, W. W. Norton & Co. New York, 1993, pp. 150, 152-154;
W. H. Brock, The Norton History of Chemistry, W. W. Norton & Co. New York, 1993, p. 469.
J. W. Servos, Physical Chemistry from Ostwald to Pauling, Princeton University Press, Princeton, 1990, p. 17;
J. W. Servos, Physical Chemistry from Ostwald to Pauling, Princeton University Press, Princeton, 1990, pp. 4-5;
J. W. Servos, Physical Chemistry from Ostwald to Pauling, Princeton University Press, Princeton, 1990, pp. 288-290;
J. W. Servos, J. Chem. Educ. 1984, 61, 5.
W. C. Bray, G. E. K. Branch, J. Am. Chem. Soc. 1913, 35, 1440.
G. N. Lewis, J. Am. Chem. Soc. 1913, 35, 1448.
J. Thomson, Philos. Mag. 1914, 27, 757.
M. Chayut, Ann. Sci. 1991, 48, 527;
W. A. Noyes, J. Am. Chem. Soc. 1917, 39, 879.
G. N. Lewis, J. Am. Chem. Soc. 1916, 38, 762.
I. Langmuir, J. Am. Chem. Soc. 1919, 41, 868.
For the multidirectional impact of the Lewis model, see: W. B. Jensen, J. Chem. Educ. 1984, 61, 191;
For the role of Lowry in advancing the idea of dative-bonding contributions to electron-pair bonds, see: D. A. Davenport, Bull. Hist. Chem. 1996, 19, 13-18;
See Ref. [5] in Davenport's paper on the letter from Born to Einstein describing the frustration to understand bonding between two neutral atoms.
W. Heitler, F. London, Z. Phys. 1927, 44, 455, English Translation H. Hettema, Quantum Chemistry Classic Scientific Paper, World Scientific, Singapore, 2000, p. 140.
F. London, Z. Phys. 1928, 46, 455.
L. Pauling, J. Am. Chem. Soc. 1931, 53, 1367;
L. Pauling, J. Am. Chem. Soc. 1931, 53, 3225;
L. Pauling, The Nature of the Chemical Bond, Cornell University Press, Ithaca, New York, 1939 (3rd edition, 1960).
J. C. Slater, Phys. Rev. 1931, 37, 481;
J. C. Slater, Phys. Rev. 1932, 41, 255.
The electronegativity concept was probably originated by Abegg, who called it “Elektroaffinität”: R. Abegg, G. Bondländer, Z. Anorg. Chem. 1899, 20, 453.
Unitary transformations convert delocalized molecular orbitals to localized ones, among which are bond orbitals. See
C. Edmiston, K. Ruedenberg, Rev. Mod. Phys. 1963, 35, 457;
C. Edmiston, K. Ruedenberg, J. Phys. Chem. 1964, 68, 1628.
Lewis further formulated dative and coordinative bonds in his 1923 monograph, in which he alludes to Werner's formulation of the coordinative bond in coordinative transition-metal complexes. See G. N. Lewis, Valence and the Structure of Atoms and Molecules, American Chemical Society Monograph Series, Book Department, The CHEMICAL CATALOG COMPANY, Inc. New York, 1923. See e.g., p. 87 in chapter VI, pp. 97-103 in Chapter VIII, and pp. 104-113 in Chapter IX.
The first description of a dative/coordinative bond of carbon in hexaphenylcarbodiphosphorane was given by Kaska et al.: W. C. Kaska, D. K. Mitchell, R. F. Reicheldfeder, J. Organomet. Chem. 1973, 47, 391;
Subsequently, the dative bond was extended to a variety of molecules: G. Frenking, R. Tonner, S. Klein, N. Takagi, T. Shimizu, A. Krapp, K. K. Pandey, P. Parameswaran, Chem. Soc. Rev. 2014, 43, 5106;
A Lewis type formulation of the dative/coordinative bond appeared in: D. Himmel, I. Krossing, A. Schnepf, Angew. Chem. Int. Ed. 2014, 53, 6047;
Angew. Chem. 2014, 126, 6159.
“Bonds and Intermolecular Interactions-The Return of Cohesion to Chemistry” by S. Shaik, in Intermolecular Interactions in Crystals: Fundamentals of Crystal Engineering (Ed.: J. J. Novoa), The Royal Society of Chemistry, London, 2017, Chapter 1, p. 3-68. Note that we exclude the less stable ionic structure (for example, F+H−), and a putative bond due to resonance between the ionic structures (which occurs as an excited state). This leaves three independent variables as in the triangle in Figure 1 d.
For a perspective, see: S. Shaik, D. Danovich, W. Wu, P. C. Hiberty, Nat. Chem. 2009, 1, 443.
For a formulation of charge-shift bonding from MO-based theory, see: H. Zhang, D. Danovich, W. Wu, B. Braïda, P. C. Hiberty, S. Shaik, J. Chem. Theory Comput. 2014, 10, 2410.
D. S. Levine, P. R. Horn, Y. Mao, M. Head-Gordon, J. Chem. Theory Comput. 2016, 12, 4812;
D. S. Levine, M. Head-Gordon, Proc. Natl. Acad. Sci. USA 2017, 114, 12649. Note that the EDA program has two options for the open-shell reference state: one is “frz”, which produces a high-spin triplet reference, the other is the spin-coupling option “sc”, which produces a singlet-pair akin to the covalent structure.
R. F. W. Bader, T. T. Nguyen-Dang, Adv. Quantum Chem. 1981, 14, 63;
C. F. Matta, R. F. W. Bader, J. Phys. Chem. A 2006, 110, 6365;
C. F. Matta, J. Comput. Chem. 2010, 31, 1297-1311.
S. Jenkins, S. R. Kirk, A. Guevara-Garcia, P. W. Ayers, P. Echegaray, E. A. Toro-Labbe, Chem. Phys. Lett. 2011, 510, 18.
X. Bin, T. Xu, S. R. Kirk, S. Jenkins, Chem. Phys. Lett. 2019, 730, 506.
B. Silvi, A. Savin, Nature 1994, 371, 683;
R. Llusar, A. Beltran, J. Andres, S. Noury, B. Silvi, J. Comput. Chem. 1999, 20, 1517.
S. Shaik, D. Danovich, B. Silvi, D. L. Lauvergnat, P. C. Hiberty, Chem. Eur. J. 2005, 11, 6358.
S. Radenković, D. Danovich, S. Shaik, P. C. Hiberty, B. Braïda, Comput. Theor. Chem. 2017, 1116, 195.
S. Shaik, D. Danovich, B. Braïda, W. Wu, P. C. Hiberty, Struct. Bonding 2016, 170, 169-212 (The Chemical Bond II, 100 Years Old and Getting Stronger).
For other papers on CSB, see:
G. Sini, S. Shaik, P. Maître, G. Sini, P. C. Hiberty, J. Am. Chem. Soc. 1992, 114, 7861;
G. Sini, P. Maitre, P. C. Hiberty, S. S. Shaik, J. Mol. Struct. THEOCHEM 1991, 229, 163;
D. L. Lauvergnat, P. C. Hiberty, D. Danovich, S. Shaik, J. Phys. Chem. 1996, 100, 5715;
A. Shurki, P. C. Hiberty, S. Shaik, J. Am. Chem. Soc. 1999, 121, 822;
J. M. Galbraith, E. Blank, S. Shaik, P. C. Hiberty, Chem. Eur. J. 2000, 6, 2425;
E. Ploshnik, D. Danovich, P. C. Hiberty, S. Shaik, J. Chem. Theory Comput. 2011, 7, 955.
In the HF wave function, the weights of covalent and ionic structures are identical. The covalent structure has full (i.e., maximal) static correlation. See Ref. [22].
S. Shaik, P. C. Hiberty, A Chemist's Guide to Valence Bond Theory, Wiley, Hoboken, 2008, Chapter 3, pp. 55-59.
M. Filatov, S. Shaik, Chem. Phys. Lett. 1999, 304, 429;
I. D. P. R. Moreira, R. Costa, M. Filatov, F. Illas, J. Chem. Theory Comput. 2007, 3, 764.
L. Gagliardi, D. G. Truhlar, G. L. Manni, R. K. Carlson, C. E. Hoyer, J. L. Bao, Acc. Chem. Res. 2017, 50, 66.
The diffuseness of the bonding orbitals affects the RECS as well. See: C. J. Laconsay, A. M. James, J. M. Galbraith, J. Phys. Chem. A 2016, 120, 8430-84384.
W. Wu, J. Gu, J. Song, S. Shaik, P. C. Hiberty, Angew. Chem. Int. Ed. 2009, 48, 1407;
Angew. Chem. 2009, 121, 1435.
S. Shaik, Z. Chen, W. Wu, A. Stanger, D. Danovich, P. C. Hiberty, ChemPhysChem 2009, 10, 2658.
W. Kutzelnigg in Theoretical Models of Chemical Bonding, (Ed. Z. B. Maksic), Springer, New York, 1990, part 2, p. 1-44;
K. Ruedenberg, Rev. Mod. Phys. 1962, 34, 326;
M. J. Feinberg, K. Ruedenberg, J. Chem. Phys. 1971, 54, 1495;
C. Q. Wilson, W. A. Goddard III, Theor. Chim. Acta. 1972, 26, 195;
A. Rozendaal, E. J. Baerends, Chem. Phys. 1985, 95, 57;
K. Ruedenberg, M. Schmidt, J. Comput. Chem. 2007, 28, 391;
F. M. Bickelhaupt, E. J. Baerends, Rev. Comput. Chem. 2000, 15, 1.
P. C. Hiberty, R. Ramozzi, L. Song, W. Wu, S. Shaik, Faraday Discuss. 2007, 135, 261.
P. Su, L. Song, W. Wu, S. Shaik, P. C. Hiberty, J. Phys. Chem. A 2008, 112, 2988.
A. Fiorillo, J. M. Galbraith, J. Phys. Chem. A 2004, 108, 5126;
A. M. James, C. J. Laconsay, J. M. Galbraith, J. Phys. Chem. A 2017, 121, 5190.
R. Hoffmann, Angew. Chem. Int. Ed. Engl. 1982, 21, 711;
Angew. Chem. 1982, 94, 725.
C. Migliorini, E. Prociatti, M. Luczkorski, D. Valensin, Coord. Chem. Rev. 2012, 256, 352;
M. T. Rodgers, P. B. Armentrout, Chem. Rev. 2016, 116, 5642;
M. T. Rodgers, P. B. Armentrout, Acc. Chem. Res. 2004, 37, 989;
I. Onyido, A. R. Norris, E. Buncel, Chem. Rev. 2004, 104, 5911;
G. Wang, B. L. Gaffney, R. A. Jones, J. Am. Chem. Soc. 2004, 126, 8908.
R. J. Hach, R. E. Rundle, J. Am. Chem. Soc. 1951, 73, 4321;
G. C. Pimentel, J. Chem. Phys. 1951, 19, 446.
V. I. Pepkin, Y. A. Lebedev, A. Y. Apin, Zh. Fiz. Khim. 1969, 43, 1564.
C. A. Coulson, J. Chem. Soc. 1964, 1442.
B. Braïda, P. C. Hiberty, Nat. Chem. 2013, 5, 417.
B. Braïda, T. Ribeyre, P. C. Hiberty, Chem. Eur. J. 2014, 20, 9643.
For an early qualitative prediction, see: S. S. Shaik, in An Encomium to Linus Pauling. Molecules in Natural Science and Medicine (Eds.: Z. B. Maksic, M. E. Maksic, Ellis Horwood, 1991, pp. 253-266.
For a VB investigation of 3c/4e π-systems, see: A. DeBlase, M. Licata, J. M. Galbraith, J. Phys. Chem. A 2012, 112, 12806-12811.
M. Messerschmidt, S. Scheins, L. Grubert, M. Patzel, G. Szeimies, C. Paulmann, P. Luger, Angew. Chem. Int. Ed. 2005, 44, 3925;
Angew. Chem. 2005, 117, 3993.
P. Coppens, Angew. Chem. Int. Ed. 2005, 44, 6810;
Angew. Chem. 2005, 117, 6970;
P. Coppens, X-ray densities and chemical bonding, Oxford University Press, New York, 1997.
V. R. Hathwar, M. K. Thomsen, M. A. H. Mamkhel, M. O. Filso, J. Overgaard, B. B. Iversen, J. Phys. Chem. A 2016, 120, 7510-7518.
See experimental analysis of the nature of Mn-Mn, Mn-Co, and other coordinative bonds: R. Bianchi, G. Gervasio, D. Marabello, Inorg. Chem. 2000, 39, 2360-2366.
V. Polo, J. Andres, B. Silvi, J. Comput. Chem. 2007, 28, 857.
For a variety of bonds to He, see: H. Rzepa, Nat. Chem. 2010, 2, 390-393.
For example,
experimental and computational data of binary alloys (GeTe)m-(Sb2Te3)n used for rewritable optical data storage discs show that the Ge-Te, Sb-Te, and Te-Te bonds apparently qualify as CSBs. See: V. G. Orlov, G. S. Sergeev, Solid State Commun. 2017, 258, 7-10;
Similarly in bismuth chalcogenides, iron pnictides, cuprates, and other unconventional superconductors, the Se−Se, Te−Te, Bi−Se, Bi−O, Sr−O, Cu−O, Fe−As, etc. appear as CSBs: V. G. Orlov, G. S. Sergeev, Phys. B 2018, 536, 839-842.
For the I−O bond see, S. Berski, Z. Latajka, A. J. Gordon, Chem. Phys. Lett. 2011, 506, 15-21.
For CSB in [FAAF]− (A=O, S, S, Se, Te) see, L. J. A. Gámez, M. Yanez, J. Chem. Theory Comput. 2013, 9, 5211-5215.
Some C-halogen bonds in dimethylhalonium ylides were characterized as CSB: A. Jubert, N. Okulik, M. del C. Michelini, C. J. A. Mota, J. Phys. Chem. A 2008, 112, 11468-11480.
The bonding in radical π-dimers was characterized as CSB. See, Y.-H. Tian, M. Kertesz, J. Phys. Chem. A 2011, 115, 13942-13949.
The O−O bonds in XO−OX (X=H, O) and the central C−C bond in small propellanes were characterized as BSBs. See: Y. Yang, J. Phys. Chem. A 2012, 116, 10150-10159.
J. L. Casals-Sainz, F. Jimenez-Gravalos, E. Francisco, A. M. Pendas, Chem. Commun. 2019, 55, 5071.
The lengthening of the F−F bond by the lone-pair repulsion was discussed in: D. Lauvergnat, P. C. Hiberty, J. Mol. Struct. THEOCHEM 1995, 338, 283. Based on the linear correlation of Req(X-X) vs. the atomic radius of X, the authors predicted that R(F−F)=1.22 Å would be the expected F−F bond length if the Pauli repulsion of the lone pairs with the bond-pair diminish.
L. Zhang, F. Ying, W. Wu, P. C. Hiberty, S. Shaik, Chem. Eur. J. 2009, 15, 2979.
In H3N-CH3+ the Laplacian is negative [-0.5116 for VBSCF and −0.3672 for MP2 calculations with 6-31G(d,p) basis set], due to a very large negative value of Lap(res) and a high contribution of the covalent structure to binding.
R. F. W. Bader, J. Chem. Phys. 1980, 73, 2871.
P. W. Ayers, S. Jenkins, J. Chem. Phys. 2009, 130, 154104.
F. E. Bartoszek, D. M. Manos, J. C. Polanyi, J. Chem. Phys. 1978, 69, 933.
S. V. O'Neal, H. F. Schaefer III, C. F. Bender, Proc. Natl. Acad. Sci. USA 1974, 71, 104;
T. H. Dunning, Jr, J. Phys. Chem. 1984, 88, 2469;
C. F. Bender, B. J. Garrison, H. F. Schaefer III, J. Chem. Phys. 1975, 62, 1188;
A. F. Voter, W. A. Goddard III, J. Chem. Phys. 1981, 75, 3638;
K. D. Dobbs, C. A. Dixon, J. Phys. Chem. 1993, 97, 2085.
P. C. Hiberty, C. Megret, L. Song, W. Wu, S. Shaik, J. Am. Chem. Soc. 2006, 128, 2836.
W. T. Borden, R. Hoffmann, T. Stuyver, B. Chen, J. Am. Chem. Soc. 2017, 139, 9010.
As was recently shown, the three-electron bonds of many species including O2, are charge-shift bonded: D. Danovich, C. Foroutan-Nejad, P. C. Hiberty, S. Shaik, J. Phys. Chem. A 2018, 122, 1873.
For a review, see: Y. Apeloig, in The Chemistry of Organic Silicon Compounds, Vol. 1 (Eds. Y. Apeloig, Z. Rappoport), Wiley, Chichester, 1989, Chapter 2.
For studies of the elusive R3Si+ cation in condensed phases vs. the accessible R3C+ cation, see:
Y. Apeloig, A. Stanger, J. Am. Chem. Soc. 1987, 109, 272;
J. B. Lambert, L. Kania, S. Zhang, Chem. Rev. 1995, 95, 1191;
A. H. Gomes de Mesquita, C. H. MacGillavry, K. Eriks, Acta Crystallogr. 1965, 18, 437;
For a recent “bottling” of tert-Butyl cation, see: T. Kato, A. Reed, Angew. Chem. Int. Ed. 2004, 43, 2908;
Angew. Chem. 2004, 116, 2968;
G. K. S. Prakash, S. Keyaniyan, S. K. R. Aniszfeld, L. Heiliger, G. A. Olah, R. C. Stevens, H.-K. Choi, R. Bau, J. Am. Chem. Soc. 1987, 109, 5123;
For sticky [Si-F-Si]+ bonds, see: N. Lühmann, H. Hirao, S. Shaik, T. Müller, Organometallics 2011, 30, 4087-4096.
R. J. P. Corriu, M. Henner, J. Organomet. Chem. 1974, 74, 1.
R. Gershoni-Poranne, P. Chen, Chem. Eur. J. 2017, 23, 4659.
Y. Wei, G. N. Sastry, H. Zipse, J. Am. Chem. Soc. 2008, 130, 3473;
E. Larionov, H. Zipse, Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2011, 1, 601.
R. J. Mulder, C. F. Guerra, F. M. Bickelhaupt, J. Phys. Chem. A 2010, 114, 7604;
J. M. Ruiz, C. F. Guerra, F. M. Bickelhaupt, J. Phys. Chem. A 2011, 115, 8310.
A. B. Patil, B. M. Bhanage, Phys. Chem. Chem. Phys. 2016, 18, 15783.
For influencing catalytic power by ligands possessing CBS, see: D. Ma, C. Zheng, Z-.N. Chen, X. Xu, Phys. Chem. Chem. Phys. 2017, 19, 2417-2424.
L. Rincón, R. Almeida, J. Phys. Chem. A 1998, 102, 9244.
L. Zhao, M. Hermann, W. H. E. Schwarz, G. Frenking, Nat. Rev. 2019, 3, 48.
See, for example, P. Levi, The Periodic Table, Chapter 5 (on potassium), Schocken Books Inc., New York, 1984, p. 61: “The differences can be small, but they can lead to radically different consequences, like a railroad's switch points; the chemist's trade consists in good part in being aware of these differences, knowing them close up, and foreseeing their effects. And not only the chemist's trade.”;
Roald Hoffmann writes about the importance of diversity in several places: In his lecture in 2017 during the award of the Primo Levi Prize, given to him by the German and the Italian Chemical Societies, he speaks about diversity in chemistry, wherein tiny little differences may make the molecules behave in extremely different ways. Thus, writes Hoffmann “only one oxygen atom has to be removed from pseudoephedrine, a decongestant, to make methamphetamine, a dangerous drug”. In his essay with Shira Leibowitz and in their book, the two authors talk in praise of impurity and diversity, which make different substances be “the same and not the same.” Often times, small changes may create qualitatively different materials : R. Hoffmann, S. Leibowitz, “Pure/Impure.” New England Review (1990-), 1994, 16, 41. JSTOR, http://www.jstor.org/stable/40242764;
R. Hoffmann, S. Leibowitz, Schmidt, Old Wine, New Flasks, W. H. Freeman and Company, New York, 1997, Chapter 7, pp. 239-292.
Similarly, consider the statement “… the value of the heuristic is judged by the degree to which it is explanatory, and furthermore, predictive of molecular properties”, in: P. Chen, R. Gershoni-Poranne, Chem. Eur. J. 2017, 23, 18325-18329.
For a recent application of the reduced density gradient (RDG) to characterize bonding, including CSB, see: R. A. Boto, J. P. Piquemal, J. Contreras-García, Theor. Chem. Acc. 2017, 136, 139.
For ELF description of 3e/2c bonds as CSBs, see: L. Fourré, B. Silvi, Heteroat. Chem. 2007, 18, 135-160.
For identification of CSB character from isodesmic reactions, see: R. Gershoni-Poranne, A. Stanger, ChemPhysChem 2012, 13, 2377-2381.
For the characterization (using ELF and AIM) of O−O bonds of six dioxetanones as CSBs and showing how this character dominates the mechanisms of decomposition of these molecules, see, L. P. de Sliva, J. C. G. E. da Silva, Struct. Chem. 2014, 25, 1075-1081.
For CSB characterization of protonated alcohols, see: P. Anderson, A. Petit, J. Ho, M. P. Mitoraj, M. L. Coote, D. Danovich, S. Shaik, B. Braida, D. H. Ess, J. Org. Chem. 2014, 79, 9998-10001.
For a fascinating interconversion of a covalent bond to CSB in silacyclo[1.1.0]butanes, see: S. Chinaroj, T. Iwamoto, J. Phys. Org. Chem. https://doi.org/10.1002/poc.4019.