A Computational Study on 18+δ Organometallics

Description:

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.

Creator(s): Yu, Liwen
Creation Date: May 2002
Partner(s):
UNT Libraries
Collection(s):
UNT Theses and Dissertations
Usage:
Total Uses: 120
Past 30 days: 6
Yesterday: 0
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Publisher Info:
Publisher Name: University of North Texas
Place of Publication: Denton, Texas
Date(s):
  • Creation: May 2002
  • Digitized: July 26, 2007
Description:

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.

Degree:
Level: Master's
Discipline: Chemistry
Language(s):
Subject(s):
Keyword(s): Computational | organometallics | DFT | 18+δ
Contributor(s):
Partner:
UNT Libraries
Collection:
UNT Theses and Dissertations
Identifier:
  • OCLC: 54888968 |
  • ARK: ark:/67531/metadc3101
Resource Type: Thesis or Dissertation
Format: Text
Rights:
Access: Public
License: Copyright
Holder: Yu, Liwen
Statement: Copyright is held by the author, unless otherwise noted. All rights reserved.