The geometrical and electronic structures of the recently synthesized dicoordinated phosphenium cations featuring a SPN bond and their corresponding three-coordinated chlorophosphine precursors are investigated theoretically by using the MNDO method. The calculated results show that the chemical bonds in the dicoordinated phosphenium cations are different from those in the corresponding three-coordinated phosphorus systems: in the former the conjugated systems containing the phosphorus atom are formed, which results in many special characteristics. To elucidate the 31P NMR chemical shifts of the dicoordinated phosphenium cations, a simple relationship, which includes a term containing not only the net atomic charge at phosphorus, but also the net atomic charges at nitrogen and sulfur, is introduced in this paper. It is shown that the relationship is quite satisfactory for predicting the 31P NMR chemical shifts of this class of phosphenium cation. Finally, the reliability of the results obtained from the MNDO calculations is tested and compared with the results obtained from ab initio RHF calculations with a 6-31G** basis set.
|Number of pages||10|
|Journal||Journal of Molecular Structure: THEOCHEM|
|State||Published - Nov 20 1995|
Bibliographical noteFunding Information:
This project was supported by the Excellent University Teacher’s Foundation of the State Education Commissiona nd the National Natural ScienceF oundation of China.
ASJC Scopus subject areas
- Condensed Matter Physics
- Physical and Theoretical Chemistry