A Computational Study on 18+δ Organometallics

• Main Author: Yu, Liwen
• Other Authors: Schwartz, Martin
• Format: Others
• Language: English
• Published: University of North Texas 2002
• Subjects: Organometallic compounds.; Computational; organometallics; DFT; 18+δ
• Online Access: https://digital.library.unt.edu/ark:/67531/metadc3101/

The B3LYP density functional has been used to calculate properties of organometallic complexes of Co(CO)3 and ReBr(CO)3, with the chelating ligand 2,3-bisphosphinomaleic anhydride, in 19- and 18-electron forms. The SBKJC-21G effective core potential and associated basis set was used for metals (Co/Re) and the 6-31G* basis set was used for all other elements. The differences of bond angles, bond distances, natural atomic charges and IR vibrational frequencies were compared with the available experimental parameters. The differences between the 19- and 18-electron systems have been analyzed. The results reveal that the 19th electron is mostly distributed over the ligand of 2,3-bisphosphinomaleic anhydride, although partially localized onto the metal fragment in 1 and 2*. Two different methods, IR-frequencies and natural atomic charges, were used to determine the value of δ. Present computed values of δ are compared with available experimental values, and predictions are made for unknown complexes.