The effects of N-heterocyclic ligands on the nature of the Ru–(NO) bond in ruthenium tetraammine nitrosyl complexes
Summary: Quantum chemical calculations at the DFT level have been carried out to analyze quantitatively the RuII–(NO)+, RuIII–(NO)0 and RuII–(NO)0 bonds in trans-[RuII(NH3)4(L)(NO)]q and trans-[RuII(NH3)4(L)(NO)]q−1 complexes, where L = 4-picoline (4-pic), C-bound imidazole (imC), N-bound imidazole...
| Permalink: | http://skupni.nsk.hr/Record/nsk.NSK01000733113/Details |
|---|---|
| Matična publikacija: |
Croatica chemica acta 82 (2009), 1 ; str. 219-232 |
| Glavni autor: | Caramori, Giovanni F. (-) |
| Ostali autori: | Frenking, Gernot (-) |
| Vrsta građe: | Članak |
| Jezik: | eng |
| Predmet: | |
| Online pristup: |
Croatica Chemica Acta |
| LEADER | 02695caa a2200301 ir4500 | ||
|---|---|---|---|
| 001 | NSK01000733113 | ||
| 003 | HR-ZaNSK | ||
| 005 | 20180918145019.0 | ||
| 007 | ta | ||
| 008 | 100413s2009 ci ||| ||eng | ||
| 035 | |9 (HR-ZaNSK)735731 | ||
| 035 | |a (HR-ZaNSK)000733113 | ||
| 040 | |a HR-ZaNSK |b hrv |c HR-ZaNSK |e ppiak | ||
| 041 | 0 | |a eng |b hrv | |
| 042 | |a croatica | ||
| 080 | |a 54 |2 MRF 1998. | ||
| 100 | 1 | |a Caramori, Giovanni F. | |
| 245 | 1 | 4 | |a The effects of N-heterocyclic ligands on the nature of the Ru–(NO) bond in ruthenium tetraammine nitrosyl complexes / |c Giovanni F. Caramori and Gernot Frenking. |
| 300 | |b Ilustr. | ||
| 504 | |a Bibliografija: 36 jed. | ||
| 504 | |a Sažetak | ||
| 520 | 8 | |a Summary: Quantum chemical calculations at the DFT level have been carried out to analyze quantitatively the RuII–(NO)+, RuIII–(NO)0 and RuII–(NO)0 bonds in trans-[RuII(NH3)4(L)(NO)]q and trans-[RuII(NH3)4(L)(NO)]q−1 complexes, where L = 4-picoline (4-pic), C-bound imidazole (imC), N-bound imidazole (imN), nicotinamide (nic), pyridine (py), and pyrazine (pz). Equilibrium geometries and the vibrational frequencies are reported for the ground state GS and light-induced metastable states, MS1 and MS2, presenting good agreement with the experimental data. The nature of the RuII–(NO)+ and RuII–(NO)0 bonds was investigated by means of the energy decomposition analysis, EDA. The Ru–(NO) bonding situation has been analyzed in two different situations: prior and after one-electron reduction at the NO+ group. The EDA results for the complexes prior to the reduction of the NO+ indicate that the metalligand π-orbital interactions between NO+ and the [RuII(NH3)4(L)]q−1 are the most important term and that the trans-ligands imN and nic contribute to an increase in the π-donor strength of the metal centre towards NO+. For RuIII–(NO)0 bonds, the smallest values of ΔEint, ΔEPauli, ΔEelstat, and De are observed when L = imC or L = nic, independent of the state under consideration, GS or MS1, indicating that when L = imC or nic the RuIII–(NO)0 bond in GS or in MS1 states is more labile. After the reduction of the NO+ group, the RuII–(NO)0 becomes more labile when the trans-ligand is imC, which agrees with the experimental rate constants of NO0 dissociation | |
| 653 | 0 | |a Kvantno-kemijski računi |a Kompleksni spojevi |a Rutenij |a Heterociklički spojevi |a Dušikovi spojevi |a Nitrozo-spojevi |a Ligand | |
| 700 | 1 | |a Frenking, Gernot | |
| 773 | 0 | |t Croatica chemica acta |x 0011-1643 |g 82 (2009), 1 ; str. 219-232 |w nsk.(HR-ZaNSK)000001621 | |
| 981 | |b B01/09 |p CRO | ||
| 998 | |a rado100413 |c vol2o130424 |b mili1809 | ||
| 856 | 4 | 2 | |u http://hrcak.srce.hr/cca |y Croatica Chemica Acta |