An Investigation into the Bonding of Copper(I) Macrocycles to Fifth Ligands

Author: Allison, Judith Lee

Year: 1979

Degree: Dissertation (Ph.D.)

Advisor: Gagné, Robert R.

Committee Member: Unknown, Unknown

Option: Chemistry

DOI: 10.7907/yz9j-9e70

Abstract

The properties and reactivities of an unusual copper(I) macrocyclic complex have been investigated. The complex, Cu(LBF₂) ([l,l-difluoro- 4,S,ll,12-tetramethyl-l-bora-3,6,10,13-tetraaza-2,14-dioxo-cyclo-tetradeca-3,S,10,12-tetraenato]copper(I)), reacts with carbon monoxide to form an isolable complex, Cu(LBF₂)CO. The crystal structure of Cu(LBF₂)CO, which was previously determined, shows a square-pyramidal geometry around copper(I) with an apical carbon monoxide and four basal nitrogens.

The crystal and molecular structure of the four-coordinate complex, Cu(LBF2), was determined. The copper binds to the four nitrogens of the macrocycle in a distorted square-planar array. The nitrogens are twisted toward a tetrahedron with resulting dihedral angles of 23 and 27° between the two sets of planes defined by copper and two adjacent nitrogens. The amount of the tetrahedral distortion is limited by the macrocycle's steric limitations.

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