Hydrazine-mediated strongly coupled Re(CO)3 dimers.
Dalton Trans
; 44(39): 17268-77, 2015 Oct 21.
Article
en En
| MEDLINE
| ID: mdl-26374670
ABSTRACT
Dimeric metal complexes can often exhibit coupling interactions via bridging ligands. In this report, we present two Re(CO)3 dimers, where the metals are linked via a bis(pyca) hydrazine (pyca = pyridine-2-carbaldehyde imine) Schiff base ligand. For the dimeric compounds 4 and 5, we observe strong coupling across the dimer as measured by cyclic voltammetry â¼480 mV separations between the first and the second reduction waves that correspond to comproportionation constants close to 1.5 × 10(8). Evidence for a mixed valence state upon one electron reduction was also observed by spectroelectrochemistry in which a clear inter-valence charge-transfer (IVCT) band was observed in [4]- and [5]-complexes. The electronic structures of all target compounds were probed by DFT and TDDFT computational methods. DFT calculations indicate that reduction takes place at the diimine units, and that the observed coupling is a ligand-based phenomenon, rather than one that involves metal-based orbitals.
Texto completo:
1
Banco de datos:
MEDLINE
Asunto principal:
Oxígeno
/
Rutenio
/
Carbono
/
Complejos de Coordinación
/
Hidrazinas
Idioma:
En
Año:
2015
Tipo del documento:
Article