Assessment of the. pi. -acceptor capability of selected ligands based on the photoelectron spectra of ruthenium ammine complexes
Journal Article
·
· Inorg. Chem.; (United States)
ESCA spectra have been recorded for a series of Ru/sup II/ and Ru/sup III/ ammine complexes of general formula ((NH/sub 3/)/sub 5/RuL)X/sub n/ (X/sup -/ = PF/sub 6//sup -/, Cl/sup -/). Binding energy regions of the C/sub 1s/, Ru/sub 3d3/s/, and Ru/sub 3d5/s/, and Ru/sub 3p3/2/ photopeaks were studied. Binding energies were determined by using nonlinear-least-squares curve fitting. ..delta.. equal to the binding energy difference for (C/sub 1s/ - Ru/sub 3d5/2/) has been used to assign a fractional increase in charge at the Ru/sup II/ center when L = a series of ..pi..-acceptor ligands: N-methylpyrazinium (CH/sub 3/pz/sup +/), CO dimethyl acetylenedicarboxylate ester (dmad), CO, pyrazine (pz), pyridine (py), and CH/sub 3/CN. Authentic Ru/sup II/ and Ru/sup III/ oxidation states were assumed for (Ru(en)/sub 3/)ZnCl/sub 4/, ..delta.. = 5.1 eV, and (Ru(NH/sub 3/)/sub 6/)Cl/sub 3/, ..delta.. = 2.5 eV, respectively. The ..pi..-acceptor order and effective Ru oxidation state were determined to be as follows: CH/sub 3/pz/sup +/, 3.01 > CO, 2.88 > dmad, 2.73 > pz, 2.51 > CH/sub 3/CN, 2.31 > py, 2.20. ..delta.. was also found to be linear in the value of E/sub 1/2/ for the (NH/sub 3/)/sub 5/RuL/sup 3+/2+/ couple. ..pi..-Donor ligands exhibit little influence on ..delta.. for Ru/sup III/ derivatives; ..delta.. = 2.4 +/- 0.1 eV for 3,5-dimethylpyrazole, 4-(dimethylamino)pyridine, and 4-aminopyridine.
- Research Organization:
- Univ. of Pittsburgh, PA
- OSTI ID:
- 5648539
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 26:15; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
Similar Records
New ruthenium(II) complexes with pyridylpyrazole ligands. Photosubstitution and /sup 1/H, /sup 13/C, and /sup 99/Ru NMR structural studies
The pK/sub a/ of pyraziniumpentacyanoruthenate(II), (Cn)/sub 5/Ru(pzH)/sup 2 -/
Kinetic studies of outer-sphere redox reactions of. mu. -pyrazinedecaaminediruthenium(II,II), -(II,III), and -(III,III)
Journal Article
·
Wed May 11 00:00:00 EDT 1983
· Inorg. Chem.; (United States)
·
OSTI ID:5749294
The pK/sub a/ of pyraziniumpentacyanoruthenate(II), (Cn)/sub 5/Ru(pzH)/sup 2 -/
Journal Article
·
Tue Mar 29 23:00:00 EST 1983
· Inorg. Chem.; (United States)
·
OSTI ID:5359503
Kinetic studies of outer-sphere redox reactions of. mu. -pyrazinedecaaminediruthenium(II,II), -(II,III), and -(III,III)
Journal Article
·
Thu Jul 31 00:00:00 EDT 1986
· J. Phys. Chem.; (United States)
·
OSTI ID:5458636
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AMMINES
BINDING ENERGY
COMPLEXES
DATA
ELECTRON SPECTROSCOPY
ENERGY
EXPERIMENTAL DATA
INFORMATION
LIGANDS
MOLECULAR STRUCTURE
NUMERICAL DATA
PHOTOELECTRON SPECTROSCOPY
RUTHENIUM COMPLEXES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* -- Chemical & Physicochemical Properties
AMMINES
BINDING ENERGY
COMPLEXES
DATA
ELECTRON SPECTROSCOPY
ENERGY
EXPERIMENTAL DATA
INFORMATION
LIGANDS
MOLECULAR STRUCTURE
NUMERICAL DATA
PHOTOELECTRON SPECTROSCOPY
RUTHENIUM COMPLEXES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES