Insight into metal-phosphorus bonding from analysis of the electronic structure of redox pairs of metal-phosphine complexes
(2005) New Journal of Chemistry — Vol. 29, n° 11, p. 1424-1430 (2005)
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- Abstract
- Density functional theory calculations reproduce the changes in geometry which are observed experimentally upon oxidation of a range of metal phosphine complexes. Removal of one electron from the metal leads to an increase in the M - P bond length, along with a decrease in pyramidalization at the phosphorus atom. These changes had previously been used to suggest that pi back-bonding from the metal to the P - R sigma* antibonding orbitals plays a role even in complexes of simple alkyl- and aryl-phosphines. Similar changes in geometry are found upon one electron oxidation of the simple model species Cr(CO)(5)(PR3) and Mo(CO)(5)(PR3) (R = H or Me). The analogous ammonia complexes instead undergo a decrease of the M - N bond length upon ionization, consistent with stronger sigma-bonding upon increasing the charge on the metal atom. Analysis of the electron density in the neutral and cationic species, and of the change in density ( this is the finite difference Fukui function) also shows evidence of pi back-bonding in the neutral species, and much less in the cationic form.
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Leyssens, T., Peeters, D., Orpen, A., & Harvey, JN. (2005). Insight into metal-phosphorus bonding from analysis of the electronic structure of redox pairs of metal-phosphine complexes. New Journal of Chemistry, 29(11), 1424-1430. https://doi.org/10.1039/b508219f (Original work published 2005)