caa a22 4500 60548791X CHVBK 20210128100453.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00214-015-1643-5 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1643-5 Prototypical metal-oxo bonds: the reactions of Cr(PF3)6, Fe(PF3)5, and Ni(PF3)4 with oxygen [Elektronische Daten] [Zhi Sun, Henry Schaefer III, Yaoming Xie, Yongdong Liu, Rugang Zhong] Terminally bound oxo complexes of late transition metals have been difficult to synthesize or isolate. Their scarcity is in part due to the electronic repulsion between oxo ligands and metal elements with highly occupied d orbitals. This study attempts to provide extra stability to such metal-oxo species. The prototypical metal-oxo trifluorophosphane complexes [(PF3)5CrO, (PF3)4FeO, and (PF3)3NiO] are studied here. The results are compared with the corresponding carbonyl counterparts [(CO)5CrO, (CO)4FeO, and (CO)3NiO]. Predicted bond dissociation energies are 90 (Cr-O), 83 (Fe-O), and 59 (Ni-O)kcal/mol, higher than those of their carbonyl counterparts by around 10kcal/mol. Consistent with bonding considerations and population analyses, the metal-oxo bonds are strengthened from the carbonyl to the trifluorophosphine complexes. Although the improvement is modest, it proves clearly that strong electron-withdrawing frameworks help in stabilizing metal-oxo complexes. This general idea may be utilized in further studies to seek or even design elusive terminal metal-oxo species and to keep pushing the limits of this area. In addition, improved viabilities are also found for the dioxygen-metal complexes [(PF3)5CrO2, (PF3)4FeO2, and (PF3)3NiO2], compared with their carbonyl counterparts. Springer-Verlag Berlin Heidelberg, 2015 DFT nationallicence Bond dissociation energies nationallicence Oxo-metal trifluorophosphane complexes nationallicence Dioxygen-metal trifluorophosphane complexes nationallicence Metal-oxo bonds nationallicence Sun Zhi College of Life Science and Bioengineering, Beijing University of Technology, 100124, Beijing, China aut Schaefer III Henry Center for Computational Quantum Chemistry, University of Georgia, 30602, Athens, GA, USA aut Xie Yaoming Center for Computational Quantum Chemistry, University of Georgia, 30602, Athens, GA, USA aut Liu Yongdong College of Life Science and Bioengineering, Beijing University of Technology, 100124, Beijing, China aut Zhong Rugang College of Life Science and Bioengineering, Beijing University of Technology, 100124, Beijing, China aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/4(2015-04-01), 1-12 1432-881X 134:4<1 2015 134 214 https://doi.org/10.1007/s00214-015-1643-5 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1643-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Sun Zhi College of Life Science and Bioengineering, Beijing University of Technology, 100124, Beijing, China aut NATIONALLICENCE 700 1- Schaefer III Henry Center for Computational Quantum Chemistry, University of Georgia, 30602, Athens, GA, USA aut NATIONALLICENCE 700 1- Xie Yaoming Center for Computational Quantum Chemistry, University of Georgia, 30602, Athens, GA, USA aut NATIONALLICENCE 700 1- Liu Yongdong College of Life Science and Bioengineering, Beijing University of Technology, 100124, Beijing, China aut NATIONALLICENCE 700 1- Zhong Rugang College of Life Science and Bioengineering, Beijing University of Technology, 100124, Beijing, China aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/4(2015-04-01), 1-12 1432-881X 134:4<1 2015 134 214