Please use this identifier to cite or link to this item:
http://dx.doi.org/10.18419/opus-1255
Authors: | Schmidt, H. M. Stoll, Hermann Preuss, Heinzwerner Becker, Gerd Mundt, Otto |
Title: | Coupled electron pair calculations for R–C≡E molecules (E = N, P, As or Sb) |
Issue Date: | 1992 |
metadata.ubs.publikation.typ: | Zeitschriftenartikel |
metadata.ubs.publikation.source: | Journal of molecular structure, Theochem 262 (1992), S. 171-185. URL http://dx.doi.org./10.1016/0166-1280(92)85107-V |
URI: | http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-50213 http://elib.uni-stuttgart.de/handle/11682/1272 http://dx.doi.org/10.18419/opus-1255 |
Abstract: | The effect of substituents R (R = H, H 3 C, F or H 5 C 6) on C≡E groups in alkylidyne compounds R - C ≡ E (E = N, P, As or Sb) has been studied at the level of valence electron CEPA (coupled electron pair approximation) calculations. Although the reactivities of R-C ≡ E compounds differ widely (depending on E), the isolated molecules all have surprisingly similar electronic structures. For the H, H 3,C and F species, our calculated bond lengths r e,(R- C) and r e,(C ≡E) agree well with experimental values where such are known. Along with the force constants, some trends for the changes in bond strength emerge. A plausible dependence of the dipole moments on E is observed. For benzonitrile (H 5 C 6 - C ≡N), published experimental values of the C - C( ≡ N) bond length differ. The problem is explored using several basis sets and methods to obtain a value of 1.436(10)A. The C...C( ≡P) bond length in benxylidynephosphane (H 5,C6,-C≡P) is calculated to be 1.435(10)A. Possible uncertainties of some of the experimental values are discussed. |
Appears in Collections: | 03 Fakultät Chemie |
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