|
Z. Naturforsch. 2012,
67b, 935 – 943
doi:10.5560/ZNB.2012-0161
Valence Bond Structures for the N3− Anion, the N3. Radical and the N6.− Radical Anion
1 School of Chemistry, The University of Melbourne, Victoria 3010, Australia
2 Ludwig-Maximilians University of Munich, Butenandtstr. 5–13 (D), D-81377 Munich, Germany
Reprint requests to Dr. Richard Harcourt. Fax: + 61 -3 – 9347 5180. E-mail:
r.harcourt@unimelb.edu.au
Received June 11, 2012 / published online September 20, 2012
With Heitler-London atomic orbital-type formulations of the wave functions for (fractional) electron-pair πx(NN) and πy(NN) bonds, increased-valence structures for the N3− anion and N3. radical are equivalent to resonance between familiar standard Lewis structures and singlet diradical (or ''long-bond'') Lewis structures. Theory is developed for the calculation of the polarity parameters that are associated with the one-electron πx(NN) and πy(NN) bonds in the increased-valence structures, and illustrative STO-6G estimates of their values are reported. They show that the πx and πy electrons of these bonds are strongly charge-correlated relative to each other.
The increased-valence structures for the N3− anion and the N3. radical are used to help construct increased-valence structures for the N6.− radical anion with C2h symmetry.
Key words: Lewis Structures, Valence Bond (VB), Increased-valence, N3− Anion, N3. Radical, N6.− Radical Anion
Supporting Material: