Isolable arene sandwiched copper(i) pyrazolates

Abstract

The π-acidic, trinuclear, copper(i) pyrazolate {[3,5-(CF3)2Pz]Cu}3 reacts with simple π-basic aromatic hydrocarbon compounds forming sandwich complexes of various types.

Isolable 1‐Butene Copper(I) Complexes and 1‐Butene/Butane Separation Using Structurally Adaptable Copper Pyrazolates

“…[30,43] These molecules contain highly fluorinated pyrazolates and coordinatively unsaturated metal sites, electrophilic Cu 3 -cores [31,44] and form adducts with π-donors, either with reorganization or retention of the Cu 3 -core. [33,[45][46] Compounds { [3,5- , and show the reorganization and retention of the Cu 3 -core, respectively. [28,34] During further studies on these metal pyrazolates, we discovered that .…”

“…[28] This represents an interesting and commercially important utility [1,4,29] for the class of molecules better known for their photo-luminescence, [30] and π-acid/π-base chemistry (e. g., supramolecular adduct formation with electron rich arenes such as benzene and toluene, or even C 60 ). [31][32][33][34] We also managed to isolate rare copperÀ olefin complexes such as { [3,5- )] 2 with both cis-and transoriented olefins). [28] To our knowledge, 1-butene adducts of copper(I) are extremely rare [35] and there are no structurally characterized examples in the literature.…”

Dinuclear and Trinuclear Complexes of Copper(I) and Silver(I) Supported by a Highly Fluorinated Pyrazolate [3,5‐(CF3)2Pz]– and N‐Heterocycles

“…As illustrated in Figure , it crystallized with a partially occupied benzene in the crystal lattice, which sits parallel to one of the faces of {[3,5‐(CF 3 ) 2 Pz]Cu} 3 . The tendency of {[3,5‐(CF 3 ) 2 Pz]Cu} 3 to form π‐acid/π‐base sandwich complexes are known, but they are more common with the silver analog , . The 1,8‐naphthyridine coordinates to one of the copper atoms of {[3,5‐(CF 3 ) 2 Pz]Cu} 3 using only one of its donor nitrogens.…”

“…An area of research activity in our laboratory concerns the chemistry of copper, silver and gold complexes of highly fluorinated pyrazolates , , , . For example, we have reported convenient routes to the synthesis of trinuclear {[3,5‐(CF 3 ) 2 Pz]M} 3 (M = Cu, Ag, Au) complexes (Figure , 1–3 ), and their remarkable photophysical properties .…”

“…The copper complex {[3,5‐(CF 3 ) 2 Pz]Cu} 3 exhibits bright phosphorescent emissions both in the solid state and in frozen solutions under UV excitation that can be easily fine‐ and coarse‐tuned to multiple visible colors by varying the solvent, copper adduct concentration, temperature, and the excitation wavelength , . Both copper and silver complexes form π‐acid/π‐base adducts with electron‐rich arenes as well as with C 60 forming diverse supramolecular aggregates , , , , . The silver complex {[3,5‐(CF 3 ) 2 Pz]Ag} 3 also serves as an excellent sensor for the detection of volatile aromatic hydrocarbons like benzene and toluene .…”