Please use this identifier to cite or link to this item: http://dx.doi.org/10.18419/opus-1255
|Authors:||Schmidt, H. M.|
|Title:||Coupled electron pair calculations for R–C≡E molecules (E = N, P, As or Sb)|
|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|
|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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