Reactivity of bulky tris(phenylpyrazolyl)methanesulfonate copper(I) complexes towards small unsaturated molecules

Monoanionic, Bis(pyrazolyl)methylborate [(Ph3B)CH(3,5-(CH3)2Pz)2)]− as a Supporting Ligand for Copper(I)-ethylene, cis-2-Butene, and Carbonyl Complexes

“…We have focused on the isolation of copper complexes of small, carbon-based molecules because they are of significant fundamental interest and technological importance. For example, copper­(I) ethylene adducts serve as models for copper­(I)-based ethylene receptor sites in plants, , and as reaction intermediates in copper-mediated alkene chemistry. − Copper­(I) carbonyl complexes have also attracted similar interest due to their importance in biochemistry, organic synthesis, and several industrial catalytic processes. ,− Notably, the oxychlorination of ethylene, the synthesis of methanol from syngas, and the selective removal of CO from gas mixtures are a few processes in which copper plays a key role. − While several copper ethylene and carbonyl complexes are known with tris­(pyrazolyl)­borates (including their heavier silver and gold counterparts), ,− and tris­(pyrazolyl)­methanes, − only very few examples of copper-alkene or -carbonyl adducts have been successfully stabilized and structurally characterized using the bidentate bis­(pyrazolyl)­borate and bis­(pyrazolyl)­methane system. ,, For example, the fluorinated bis­(pyrazolyl)­borate ligand supported copper­(I) alkene complexes [H 2 B­(3,5-(CF 3 ) 2 Pz) 2 ]­CuL (L = styrene, cyclooctene, 4-vinylanisole, triethylvinylstyrene) and {[H 2 B­(3,5-(CF 3 ) 2 Pz) 2 ]­Cu} 2 (1,5-COD), as well as cationic copper­(I) olefin complex {[CH 2 (3,5-(CH 3 ) 2 Pz) 2 ]­Cu­(cyclooctene)}­OTf of bis­(pyrazolyl)­methane have been reported in the literature. ,, Copper carbonyl complexes of bis­(pyrazolyl)­borate and bis­(pyrazolyl)­methane are also less numerous and include [CH 2 (3,5-(CF 3 ) 2 Pz) 2 ]­Cu­(CO)­(OTf), [CH 2 (3-(CF 3 )­Pz) 2 ]­Cu­(CO)­(OTf), [CH 2 (3,5-(CH 3 ) 2 Pz) 2 ]­Cu­(CO)­(OClO 3 ), and [{[CH 2 (3,5-(CH 3 ) 2 Pz) 2 ]­Cu­(CO)} 2 ­(μ-pyrazine)]­(ClO 4 ) as the structurally well authenticated adducts of this type. , …”

C-Homoscorpionate Oxidation Catalysts—Electrochemical and Catalytic Activity

“…A systematic investigation of the coordination behavior of new C-scorpionates, as well as some of the known ones, toward a variety of transition metals (e.g., V [44,[46][47][48][49], Mo [17,19,50], Re [51,52], Fe [44,46,49,53], Ru [54], Co [12,13], Ni [44,49,55], Pd [44], Cu [43,45,46,56,57], Ag [14], Au [58] or Zn [44,56]) followed, leading to new classes of complexes exhibiting different types of coordination modes (Figures 4 and 5). Like the pincer of a scorpion, these versatile tripodal ligands bind metal centers with nitrogen atoms from two pyrazolyl rings attached to the central carbon atom; the third pyrazolyl attached to carbon rotates forward like a scorpion's tail to "sting" the metal; hence the name of "scorpionates" (Figure 4).…”

Electrochemical Properties of (h5-C5Me5)–Rhodium and –Iridium Complexes Containing Bis(pyrazolyl)alkane Ligands

“…Poly(pyrazolyl)borates and their metal complexes are widely studied and applied in several areas of chemistry [1,2]. We have been interested [3][4][5][6][7][8][9][10] in the coordination chemistry of their much less studied carbon analogues, the poly(pyrazolyl)alkane-type scorpionates, as well as on the synthesis of new derivatives [11][12][13] either by substitution at the pyrazolyl rings or functionalization of the apical carbon, which can play a critical role for the modification of their properties.…”