Synthesis, characterization, and x-ray molecular structures of mono- and dinuclear copper complexes with 2,7-bis(2-pyridyl)-1,8-naphthyridine

Journal Article · Wed Oct 24 04:00:00 EDT 1984 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00190a041· OSTI ID:5943087

Tikkanen, W R; Krueger, C; Bomben, K D; Jolly, W L; Kaska, W C; Ford, P C

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), Journal Name: Inorg. Chem.; (United States) Vol. 23:22; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
400301 -- Organic Chemistry-- Chemical &amp; Physicochemical Properties-- (-1987)
ABSORPTION SPECTROSCOPY
AQUEOUS SOLUTIONS
AROMATICS
AZINES
BIPYRIDINES
BOND ANGLE
BOND LENGTHS
CHELATES
COHERENT SCATTERING
COMPLEXES
CONDENSED AROMATICS
COPPER COMPLEXES
CORRELATIONS
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CRYSTALLOGRAPHY
DATA
DATA ANALYSIS
DIFFRACTION
DIMENSIONS
DISPERSIONS
ELECTRON SPECTROSCOPY
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
INFORMATION
LATTICE PARAMETERS
LEAST SQUARE FIT
LENGTH
MAGNETIC PROPERTIES
MAGNETIC SUSCEPTIBILITY
MATHEMATICAL MODELS
MAXIMUM-LIKELIHOOD FIT
MIXTURES
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
NUMERICAL DATA
NUMERICAL SOLUTION
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOSPHORUS FLUORIDES
PHOTOELECTRON SPECTROSCOPY
PHYSICAL PROPERTIES
PYRIDINES
SAMPLE PREPARATION
SCATTERING
SOLUTIONS
SPACE GROUPS
SPECTROSCOPY
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY
X-RAY DIFFRACTION