Synthesis, characterization, and x-ray molecular structures of mono- and dinuclear copper complexes with 2,7-bis(2-pyridyl)-1,8-naphthyridine
The preparation and characterization of two complexes of 2,7-bis(2-pyridyl)-1,8-naphthyridine (bpnp) with copper(II) and copper(I) are described. The X-ray molecular structure of a mononuclear Cu(I) complex, (Cu(bpnp)(bis-triphenylphosphine)PF/sub 6/, was determined with full-matrix least-squares procedures to a final R index of 0.057. Crystals are monoclinic, space group P2/sub 1//n, with cell dimensions a = 14.855 (6) A, b = 21.914 (8) A, c = 15.111 (2) A, and V = 4862.651 A/sup 3/ with Z = 4. The X-ray molecular structure of the dinuclear complex (Cu/sub 2/(bpnp)(..mu..-Cl)(..mu..-OH)Cl/sub 2/) was also determined to a final R index of 0.0363. The crystals are monoclinic, space group P2/sub 1//m, with cell dimensions a = 7.694 (1) A, b = 16.434 (2) A, c = 7.921 (1) A, and V = 952.695 A/sup 3/ with Z = 2. In the latter complex, each Cu(II) ion is chelated by a 2,2'-bipyridine fragment of the bpnp and the two metal ions are linked by bridging chlorine and oxygen atoms. The Cu-Cu distance is 3.022 A. The coordination geometry about each Cu(II) is discussed. Magnetic susceptibility measurements of the paramagnetic complex suggest a weak antiferromagnetic interaction (absolute value 2J < 200 cm/sup -1/, room-temperature magnetic moment/Cu = 1.64 ..mu../sub B/), which couples the spins of the two unpaired electrons. Cyclic voltammograms of this complex in aqueous solution show reduction occurs in two one-electron transfers (E/sub 1/2/ = 0.36, 0.16 V vs. Ag/AgCl). X-ray photoelectron spectroscopy allows differentiation of bridging vs. terminal chlorine atoms with peaks at 197.2 (5) and 196.2 (2) eV, respectively. Preliminary studies show that in situ reduction of the bpnp copper(II) dimer gives solutions of bpnp copper(I) dimers that reversibly coordinate carbon monoxide. 30 references, 3 figures, 6 tables.
- Research Organization:
- Univ. of California, Santa Barbara
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5943087
- Journal Information:
- Inorg. Chem.; (United States), Vol. 23:22
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COPPER COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
ABSORPTION SPECTROSCOPY
AQUEOUS SOLUTIONS
BIPYRIDINES
BOND ANGLE
BOND LENGTHS
CHELATES
CONDENSED AROMATICS
CORRELATIONS
CRYSTALLOGRAPHY
DATA ANALYSIS
EXPERIMENTAL DATA
LATTICE PARAMETERS
LEAST SQUARE FIT
MAGNETIC SUSCEPTIBILITY
MATHEMATICAL MODELS
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
PHOSPHINES
PHOSPHORUS FLUORIDES
PHOTOELECTRON SPECTROSCOPY
SAMPLE PREPARATION
SPACE GROUPS
VOLTAMETRY
X-RAY DIFFRACTION
AROMATICS
AZINES
COHERENT SCATTERING
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
DIMENSIONS
DISPERSIONS
ELECTRON SPECTROSCOPY
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
LENGTH
MAGNETIC PROPERTIES
MAXIMUM-LIKELIHOOD FIT
MIXTURES
NUMERICAL DATA
NUMERICAL SOLUTION
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHORUS COMPOUNDS
PHYSICAL PROPERTIES
PYRIDINES
SCATTERING
SOLUTIONS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)