Syntheses, structures, and properties of copper(II) and copper(I) complexes of the new binucleating ligand 1,3-bis[bis(2-pyridylmethyl)amino]benzene

Journal Article · Wed May 27 00:00:00 EDT 1992 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00037a047· OSTI ID:6969119

Schindler, S; Szalda, D J; Creutz, C ^[1]

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1. Brookhaven National Lab., Upton, NY (United States)

The synthesis and characterization of the new copper complexes Cu[sub 2]L[prime][sub 2](H[sub 2]O)[sub 2](ClO[sub 4])[sub 4][center dot]2H[sub 2]O (VI), Cu[sub 2]L(H[sub 2]O)[sub 2](ClO[sub 4])[sub 4][center dot]4H[sub 2]O (VII), Cu[sub 2]L(CH[sub 3]CN)(PF[sub 6])[sub 2](VIII), and Cu[sub 2]L(CO)[sub 2](PF[sub 6])[sub 2] (IX) (L = 1,3-bis[bis(2-pyridylmethyl)amino]benzene, L[prime] = 1-[bis(2-pyridylmethyl)amino]-3-[(2-pyridylmethyl)amino]benzene) are described. The crystal structures of the copper complexes were determined. The copper(II) ions in VII are bridged by a perchlorate ion in the solid state. Complex VIII of formula Cu[sub 2]P[sub 2]F[sub 12]N[sub 7]C[sub 32]H[sub 31] crystallizes in the triclinic space group. The two copper(I) ions in VIII are in different environments because acetonitrile is bound to only one copper site. Complex IX of formula Cu[sub 2]P[sub 2]F[sub 12]O[sub 2]N[sub 6]C[sub 32]H[sub 28] crystallizes in the triclinic space group. The dicarbonyl complex IX is formed from the addition of two molecules of carbon monoxide to VIII. The binding constant for this reaction, measured at 22 [plus minus] 2C in dimethylformamide by cyclic voltammetry, is 2.1 [times] 10[sup 8] M[sup [minus]2] per copper(I) dimer. Cyclic voltammetry and differential pulse voltammetry show that the redox potentials for Cu[sup II]Cu[sup II] [yields] Cu[sup I]Cu[sup II] [yields] Cu[sup I]Cu[sup I] are strongly solvent dependent. Reaction of the copper(I) complex with oxygen in methanol yields the same copper(II) species as is obtained independently from the reaction of Cu[sup 2+] with L. Hydroxylation of the benzene ring of the ligand is not observed.

• DOE Contract Number: AC02-76CH00016
• OSTI ID: 6969119
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 31:11; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

550200* -- Biochemistry
59 BASIC BIOLOGICAL SCIENCES
ABSORPTION SPECTRA
BOND ANGLE
BOND LENGTHS
CHEMICAL ANALYSIS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
COPPER COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DIMENSIONS
ELECTRIC POTENTIAL
LENGTH
LIGANDS
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
ORTHORHOMBIC LATTICES
QUALITATIVE CHEMICAL ANALYSIS
REDOX REACTIONS
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRICLINIC LATTICES
VOLTAMETRY