Fluoride as a terminal and bridging ligand for copper: Isolation and x-ray crystallographic characterization of monomeric and dimeric complexes [CuII(TMPA)F]n n+ (n = 1 or 2; TMPA = tris[(2-pyridyl)methyl]amine)

Richard R. Jacobson, Zoltán Tyeklár, Kenneth D. Karlin, Jon Zubieta

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The copper(I) complex with tripodal tetradentate amine ligand TMPA, [CuI(TMPA)CH3CN]PF6 (1; TMPA = tris[(2-pyridyl)methyl]amine), reacts with dioxygen, resulting in breakdown of the hexafluorophosphate anion and providing two distinct fluoride Cu(II) complexes that have been crystallographically characterized. [CuII(TMPA)F]2(PF6)2 (2) is a fluoride doubly bridged dimer (axial-equatorial), where each copper ion is pseudooctahedrally coordinated [C36H]6Cu2F14N8P 2, monoclinic P21/n; a = 11.649 (4), b = 12.942 (4), c = 14.654 (4) Å; β = 110.67 (2)°; Z = 4, V = 2067 (1) Å3]. However, [CuII(TMPA)F]-PF6·CH2Cl2 (3a) contains a trigonal-bipyramidal (TBP) coordination environment, with axial fluoride and tertiary amine ligation [C19H20Cl2CuF7N4P, orthorhombic Pcab; a = 11.869 (2), b = 15.891 (3), c = 26.116 (6) Å; Z = 8, V = 4926 (2) Å3]. Complex 3a readily loses its dichloromethane to give [CuII(TMPA)PF6·1/2H 2O (3b), which has solution properties (i.e. UV-vis, EPR) characteristic of TBP coordination. Compound 2 breaks down in solution to give the same monomeric structure as 3b, and solution UV-vis and EPR studies indicate the 3b structure can also be directly generated by addition of fluoride ion to [CuII-(TMPA)H2O](ClO4) (4).

Original languageEnglish (US)
Pages (from-to)2035-2040
Number of pages6
JournalInorganic Chemistry
Issue number9
StatePublished - 1991


ASJC Scopus subject areas

  • Inorganic Chemistry

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