A personal reminiscence about theories used and misused in structural chemistry
Tóm tắt
In the last half-century, chemists acquired enough information about the structures and force fields of molecules to formulate what appeared to be successful theories (better called models) of molecular properties. For various reasons, chemists relied particularly heavily on studies of small hydrogen-containing compounds to shape their thinking. As discussed in the following text, this led to some inappropriate generalizations. In my first studies of molecular structure by gas-phase electron diffraction (GED), I was fortunate to find contradictions to the theories proposed at the time. What follows are reminiscences of how that came about and what happened subsequently. The main lesson to be earned, at least for molecules with central atoms that are not extremely large, is that the principal forces governing molecular structure are neither hybridization nor even the popular valence shell electron pair repulsions, explanations still taught routinely in chemistry courses but, instead, are the forces between geminal atoms resulting in the close-packing of ligands.
Tài liệu tham khảo
Bartell LSJ (1960) Chem Phys 32:827
Coppens PJ (1962) Chem Phys 36:2523
Glidewell C (1976) Inorg Chem Acta 20:113
Hargittai I (1985) The structure of volatile sulphur compounds. Reidel, Dordrecht
Hargittai M, Hargittai I (1987) Phys Chem Miner 14:413
Hargittai I (1979) Z Naturforsch 34a:755
Hargittai I (1981) J Mol Struct 77:313
Hargittai I (1979) J Mol Struct 54:287
Levy JB, Hargittai I (1998) J Mol Struct 454:127
Hargittai I, Menyhard D (2010) J Mol Struct 978:136
Pauling L (1928) Proc Natl Acad Sci USA 14:359
Pauling L (1931) Phys Rev 37:1184
Pauling L, Hayward R (1964) The architecture of molecules. W. H. Freeman & Company, San Francisco, p 26
Gallaway WS, Barker EF (1942) J Chem Phys 10:88
Bonham RA, Bartell LSJ (1959) Am Chem Soc 81:3491
Bonham RA, Bartell LS, Kohl DAJ (1959) Amer Chem Soc 81:4765
Bartell LS, Bonham RA (1960) J Chem Phys 32:824
Bartell LS (1968) J Chem Educ 15:754
Bartell LS, Bonham RA (1959) J Chem Phys 31:400
Shimanouchi T (1963) Pure Appl Chem 7:131
Shimanouchi TJ (1949)Chem Phys 17: 245, 734, 848
Urey HC, Bradley CA (1939) Phys Rev 38:1969
Burkert U, Allinger NL (1982) Molecular mechanics. ACS monograph 177. American Chemical Society, Washington
Bartell LS, Kuchitsu K (1962) J Chem Phys 37:691.8
Bartell LS, Hansen KW (1965) Inorg Chem 4:1775, 1777
Yow H, Bartell LSJ (1973) Mol Struct 15:209
Gillespie RJJ (1963) Chem Educ 41:295
Gillespie RJ, Hargittai I (1991) The VSEPR model of molecular geometry. Allyn and Bacon, Boston
Bartell LS (1966) Inorg Chem 5:1635
Bartell LS, Gavin R M Jr (1968) J Chem Phys 48:2466
Gillespie RJ (2008) Coord Chem Rev 252:1315
Gillespie RJ, Johnson SA (1997) Inorg Chem 36:3031
Robinson EA, Johnson SA, Tang T-H, Gillespie RJ (1997) Inorg Chem 36:3022
Gillespie RJ, Robinson EA (1998) Adv Mol Struct Res 4:1
Gillespie RJJ (1998) Chem Educ 75:923
Gillespie RJ, Bytheway I, Robinson EA (1998) Inorg Chem 36:2811
Robinson EA, Heard GL, Gillespie RJ (1999) J Mol Struct 485:305
Gillespie RJ, Robinson EA, Heard GL (1998) Inorg Chem 37:6884
Gillespie RJ (2000) Coord Chem Rev 197:51
Gillespie RJ, Popelier PLA (2001) Chemical bonding and molecular geometry: from Lewis to electron densities. Oxford University Press, Oxford
Robinson EA, Gillespie RJ (2003) Inorg Chem 42:3865
Bartell LSJ (1955) Chem Phys 23:1219
Bartell LS, Kuchitsu K, DeNeui RJJ (1961) Chem Phys 35:1211
Kuchitsu K, Bartell LSJ (1962) Chem Phys 36:2470
Hariharan PC, Pople JA (1974) Mol Phys 27:209
Meyer WJ (1973) Chem Phys 58:1017
Stanton JF (1999) Mol Phys 97:841
Jacob EJ, Thompson HB, Bartell LS (1967) J Chem Phys 47:3736
Fitzwater S, Bartell LS (1976) J Am Chem Soc 98:5107
Bartell LS, Bürgi HB (1972) J Am Chem Soc 94:5239