Ru(bpy)[sub 2][sup 2+] and Os(bpy)[sub 2][sup 2+] complexes of large polyaza cavity-shaped ligands
- Univ. of Houston, TX (United States)
The Friedlaender condensation of cyclic 1,2-diketones with 2-amino-5,6-dihydro-1,10-phenanthroline-3-carboxaldehyde provides a series of hexaaza cavity-shaped molecules 2a-c. Reaction with Ru(bpy)[sub 2]Cl[sub 2] (where bpy = 2,2[prime]-bipyridine) incorporates Ru(II) into a distal bidentate site. For ligands which are significantly nonplanar, a second Ru(II) or Os(II) nucleus can similarly be incorporated into the remaining distal site. The use of bpy-d[sub 8] as an auxilliary ligand simplifies the NMR spectra of the complexes and permits a detailed conformational analysis which is reinforced by an X-ray determination of the dinuclear complex [(bpy)[sub 2]Ru(2c)Ru(bpy)[sub 2]](PF[sub 6])[sub 4], which crystallizes in the monoclinic space group P2[sub 1]/n with a = 13.535(6) [Angstrom], b = 27.399(8) [Angstrom], c = 22.400(8) [Angstrom], [beta] = 96.72(3)[degrees], [mu] = 5.39 cm[sup [minus]1], and Z = 4. Communication of the metal centers through the bridging ligand is examined by electronic absorption and emission spectroscopy and electrochemical analysis. Evidence is presented for limited communication between the two halves of the bridging ligand controlled by the length of the central polymethylene bridge. 38 refs., 10 figs., 3 tabs.
- OSTI ID:
- 6044694
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 32:9; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
OSMIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
RUTHENIUM COMPLEXES
ABSORPTION
ABSORPTION SPECTROSCOPY
AROMATICS
BIPYRIDINES
CATIONS
ELECTROCHEMISTRY
EMISSION SPECTROSCOPY
LATTICE PARAMETERS
LENGTH
LIGANDS
MONOCLINIC LATTICES
NUCLEAR MAGNETIC RESONANCE
ORGANIC NITROGEN COMPOUNDS
AZINES
CHARGED PARTICLES
CHEMISTRY
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIMENSIONS
HETEROCYCLIC COMPOUNDS
IONS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
PYRIDINES
RESONANCE
SORPTION
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400400 - Electrochemistry