TY - JOUR
T1 - Nature of the Ru−NO Coordination Bond
T2 - Kohn–Sham Molecular Orbital and Energy Decomposition Analysis
AU - Orenha, Renato P.
AU - Rocha, Marcus V.J.
AU - Poater, Jordi
AU - Galembeck, Sérgio E.
AU - Bickelhaupt, F. Matthias
PY - 2017/6/1
Y1 - 2017/6/1
N2 - We have analyzed structure, stability, and Ru−NO bonding of the trans-[RuCl(NO)(NH3)4]2+ complex by using relativistic density functional theory. First, we focus on the bond dissociation energies associated with the three canonical dissociation modes leading to [RuCl(NH3)4]++NO+, [RuCl(NH3)4]2++NO, and [RuCl(NH3)4]3++NO−. The main objective is to understand the Ru−NO+ bonding mechanism in the conceptual framework of Kohn–Sham molecular orbital theory in combination with a quantitative energy decomposition analysis. In our analyses, we have addressed the importance of the synergism between Ru−NO+ σ-donation and π-backdonation as well as the so-called negative trans influence of the Cl− ligand on the Ru−NO bond. For completeness, the Ru−NO+ bonding mechanism is compared with that of the corresponding Ru−CO bond.
AB - We have analyzed structure, stability, and Ru−NO bonding of the trans-[RuCl(NO)(NH3)4]2+ complex by using relativistic density functional theory. First, we focus on the bond dissociation energies associated with the three canonical dissociation modes leading to [RuCl(NH3)4]++NO+, [RuCl(NH3)4]2++NO, and [RuCl(NH3)4]3++NO−. The main objective is to understand the Ru−NO+ bonding mechanism in the conceptual framework of Kohn–Sham molecular orbital theory in combination with a quantitative energy decomposition analysis. In our analyses, we have addressed the importance of the synergism between Ru−NO+ σ-donation and π-backdonation as well as the so-called negative trans influence of the Cl− ligand on the Ru−NO bond. For completeness, the Ru−NO+ bonding mechanism is compared with that of the corresponding Ru−CO bond.
KW - molecular orbital analysis
KW - negative trans influence
KW - nitric oxide
KW - ruthenium complexes
KW - synergy
UR - http://www.scopus.com/inward/record.url?scp=85016989173&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85016989173&partnerID=8YFLogxK
U2 - 10.1002/open.201700028
DO - 10.1002/open.201700028
M3 - Article
AN - SCOPUS:85016989173
VL - 6
SP - 410
EP - 416
JO - ChemistryOpen
JF - ChemistryOpen
SN - 2191-1363
IS - 3
ER -
