| Abstract
| - Density functional calculations have been carried out to determine the structure andbonding for ruthenium porphyrin and carbonyl diyl complexes (CO)4Ru−EHeq (1a−e),(CO)4Ru−EHax (2a−e), (Por)Ru−EH (3a−e), and for (Por)Ru−E(trip) (4a−e, trip = 2,4,6-triisopropylphenyl) with E being a group 13 element (E = B−Tl). Subsequent natural bondorbital (NBO) analyses have been applied to examine in detail the Ru−E bonding situationand the influence of the porphyrin ligand. The calculations reveal high Ru−E (E = B−Tl)bond dissociation energies, especially for the ruthenium boron bonds in 3a and 4a. The NBOanalyses show E−Ru π-back-bonding is most significant in the case of boron. The influenceof the porphyrin ligand on this π-back-bonding interaction is similar to the one demonstratedfor carbonyl ligands; however, the σ-donation from E to Ru is stronger in the case of theporphyrin ligand.
- Calculations at the DFT level for ruthenium porphyrin complexes (Por)Ru−E(trip) with E = B−Tl reveal that these species are all thermodynamically stable and are suitable targets for future syntheses.
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