A Boron-Fluorinated Tris(pyrazolyl)borate Ligand ((F) Tp*) and Its Mono- and Dinuclear Copper Complexes [Cu((F) Tp*)2 ] and [Cu2 ((F) Tp*)2 ]: Synthesis, Structures, and DFT Calculations.
Reaction of [Si(3,5-Me2 pz)4 ] (1) with [Cu(MeCN)4 ][BF4 ] (2) gave the mono- and dinuclear copper complexes [Cu2 ((F) Tp*)2 ] (3) and [Cu((F) Tp*)2 ] (4). Both complexes contain the so-far unprecedented boron-fluorinated (F) Tp* ligand ([FB(3,5-Me2 pz)3 ](-) with pz=pyrazolyl) originating from 1, acting as a pyrazolyl transfer reagent, and the [BF4 ](-) counter anion of 2, serving as the source of the {BF} entity. The solid-state structures as well as the NMR and EPR spectroscopic characteristics of the complexes were elaborated. Pulsed gradient spin echo (PGSE) experiments revealed that 3 retains (almost entirely) its dimeric structure in benzene, whereas dimer cleavage and formation of acetonitrile adducts, presumably [Cu((F) Tp*)(MeCN)], is observed in acetonitrile. The short Cu⋅⋅⋅Cu distance of 269.16 pm in the solid-state is predicted by DFT calculations to be dictated by dispersion interactions between all atoms in the complex (the Cu-Cu dispersion contribution itself is only very small). As revealed by cyclic voltammetry studies, 3 shows an irreversible (almost quasi-reversible at higher scan rates) oxidation process centred at E(pa) =-0.23 V (E(0) 1/2 =-0.27 V) (vs. Fc/Fc(+) ). Oxidation reactions on a preparative scale with one equivalent of the ferrocenium salt [Fc][BF4 ] (very slow reaction) or air (fast reaction) furnished blue crystals of the mononuclear copper(II) complex [Cu((F) Tp*)2 ] (4). As expected for a Jahn-Teller-active system, the coordination sphere around copper(II) is strongly distorted towards a stretched octahedron, in accordance with EPR spectroscopic findings.
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131, Karlsruhe, Germany.
Timo
T
Augenstein
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131, Karlsruhe, Germany.
Franziska
F
Dorner
Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131, Karlsruhe, Germany.
Kevin
K
Reiter
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131, Karlsruhe, Germany.
Hanna E
HE
Wagner
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131, Karlsruhe, Germany.
Delphine
D
Garnier
Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131, Karlsruhe, Germany.
Wim
W
Klopper
Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstr. 15, 76131, Karlsruhe, Germany. breher@kit.edu.
Frank
F
Breher
copper; dinuclear complexes; dispersion interactions; tripodal ligands; tris(pyrazolyl)borates