Acetylene and terminal alkyne complexes of copper(i) supported by fluorinated pyrazolates: syntheses, structures, and transformations

Abstract

A variety of isolable, 2 : 1 and 1 : 1 copper(i)–alkyne complexes of containing pyrazolate ligand supports are presented as well as the copper pyrazolate mediated acetylenic C–H and alkyne CC bond functionalizations.

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 .…”

“…The trinuclear copper(I) complexes {[3,5‐(CF 3 ) 2 Pz]Cu} 3 [Cu−H] 3 and {[4‐Br‐3,5‐(CF 3 ) 2 Pz]Cu} 3 [Cu−Br] 3 can be synthesized using copper(I) oxide and corresponding pyrazoles 3,5‐(CF 3 ) 2 PzH and 4‐Br‐3,5‐(CF 3 ) 2 PzH via a convenient route [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‐(CF 3 ) 2 Pz]Cu(H 2 C=CH 2 )} 2 ( [Cu−H ⋅ (C 2 H 4 )] 2 ) and {C 60 ( [Cu−H] 3 ) 4 } ∞ are two products resulting from the ethylene and C 60 interaction with [Cu−H] 3 , and show the reorganization and retention of the Cu 3 ‐core, respectively [28,34] …”

Copper(I)‐chitin biopolymer based: An efficient and recyclable catalyst for click azide–alkyne cycloaddition reactions in water

“…In order to explain the catalytic activity of the proposed catalyst in azide–alkyne cycloaddition reactions and to better understand the reaction mechanism, [ 36–44 ] density functional theory (DFT) calculations were conducted at the M062X/6‐31G(d,p) (LANL2DZ for Cu) level using water as a solvent in the CPCM model. As illustrated in Scheme 3, the model complex of the CuI‐chitin catalyst was chosen as the appropriate model for the CuI‐CHT with benzyl azide and phenyl acetylene as the starting materials for the CuAAC reaction.…”

“…In order to explain the catalytic activity of the proposed catalyst in azide-alkyne cycloaddition reactions and to better understand the reaction mechanism, [36][37][38][39][40][41][42][43][44] density functional theory (DFT) calculations were conducted at [37] 11 Cu(I)-AMPS 1 Water, r.t. 1-2 8 0 -98 Bahsis et al [18] Abbreviations: AMPS, aminomethyl polystyrene; CS, chitosan; PEG-PS, poly(ethylene glycol)-polystyrene. the M062X/6-31G(d,p) (LANL2DZ for Cu) level using water as a solvent in the CPCM model.…”

“…In fact, the reaction between the copper(I)-chitin complex and the terminal alkyne contributes to the formation of the copperacetylide complex (Scheme 3). [39][40][41][42][43][44][45][46][47] This interaction leads to the formation of the reactive complex (RC) intermediate. This step is highly exothermic in water with 4.24 kcal mol À1 (Figure S1).…”