INOR 734 |
| Although the catalytic activity of iron dinitrosyl complexes has been known for several decades, only few examples of π-bounded olefin were isolated. Variable temperature NMR study gave an activation energy barrier of ~18.1 kcal/mol for the complex, Fe(NO)2P(OCH3)3TCNE. This is higher than other published barriers for the rotation of coordinated metal olefins. DFT calculations were carried out with two different perspectives using GTO and Slater type orbitals. In both cases, hybrid functionals giving the best results, B3LYP, were used. The calculations show that the interaction of N-O and C-N does not seem to play an important role while the back-donation from the Fe(NO)2 into π* of the alkene is very strong. This back-donation is 29% from the HOFO (Fe(NO)2) to the LUFO (TCNE). Calculations at different rotation angles of TCNE show a decreasing of back-donation to almost zero when the N-O and C-N are at 90° to each other. |
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Theoretical and Computational Chemistry
7:00 PM-10:00 PM, Tuesday, August 21, 2007 BCEC -- Exhibit Hall - B2, Poster
Division of Inorganic Chemistry |