Relativistic Effects in Iron-, Ruthenium-, and Osmium Porphyrins

Authors

M.-S. Liao
Steve Scheiner, Utah State UniversityFollow

Document Type

Article

Journal/Book Title

Chemical Engineering Science

Publication Date

12-2002

Publisher

Elsevier

Volume

285

Issue

2-3

First Page

195

Last Page

206

Abstract

Nonrelativistic and relativistic DFT calculations are performed on four-coordinate metal porphyrins MP and their six-coordinate adducts MP(py)₂ and MP(py)(CO) (py=pyridine) with M=Fe, Ru, and Os. The electronic structures of the MPs are investigated by considering all possible low-lying states with different configurations of nd-electrons. FeP and OsP have a ground state, while this state is nearly degenerate with for RuP. Without relativistic corrections, the ground states of both RuP and OsP would be . For the six-coordinate adducts with py and CO, the strong-field axial ligands raise the energy of the M d_z²-orbital, thereby making the M^II ion diamagnetic. The calculated redox properties of MP(py)₂ and MP(py)(CO) are in agreement with experiment. The difference between RuP(py)(CO) and OsP(py)(CO), in terms of site of oxidation, is due to relativistic effects.

Comments

http://www.sciencedirect.com/science/article/pii/S0301010402008364

Publisher PDF is available for download through the link above.

Published by Elsevier in Chemical Engineering Science.

Recommended Citation

Relativistic Effects in Iron-, Ruthenium-, and Osmium Porphyrins M.-S. Liao, S. Scheiner Chem. Phys. 2002 285 195-206