Abstract
The bonding and geometries of H 2Fe(CO) 3, H 2Fe(CO) 3(C 2H 4), and HFe(CO) 3(C 2H 5), which are species relevant to iron carbonyl-catalyzed olefin hydrogenation, are analyzed using density functional theory (DFT). These calculations indicate that H 2Fe(CO) 3 and H 2Fe(CO) 3(C 2H 4) are respectively triplet and singlet dihydrogen complexes with H 2Fe(CO) 3(C 2H 4) lower in energy than HFe(CO) 3(C 2H 5) by a modest amount (10.2 kcal/mol with BP86/LACV3P**). Further, it is likely that when H 2Fe(CO) 3(C 2H 4) forms, it can rearrange to form the HFe(CO) 3(C 2H 5) complex. The reductive elimination of C 2H 6 from HFe(CO) 3(C 2H 5) is exothermic, whether it is accompanied by or precedes ethylene addition.
Original language | English (US) |
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Pages (from-to) | 4714-4720 |
Number of pages | 7 |
Journal | Organometallics |
Volume | 24 |
Issue number | 20 |
DOIs | |
State | Published - Sep 26 2005 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry