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

Abstract

The chemistry of trinuclear silver(I) and copper(I) pyrazolates with aromatic, bidentate N-heterocycles, 2,2′-bipyridine, 6,6′-dimethyl-2,2′-bipyridine, 1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, and 1,8-naphthyridine are presented. These N-donor ligands react readily with {[3,5-(CF 3 ) 2 Pz]Ag} 3 and {[3,5-(CF 3 ) 2 Pz]Cu} 3 providing mixed-ligand complexes with all nitrogen coordination spheres at metal in high yield. The fluorinated pyrazolate acts as a bridging ligand in these complexes. The bipyridine and phenanthroline systems with donor lone pairs at an acute angle serve as bidentate chelators for copper and silver providing dinuclear complexes. They feature planar, boat or chair shaped Ag 2 N 4 or Cu 2 N 4 cores and [a]

Effects on the magnetic interaction caused by molecular recognition in complexes of 1,2-azole-based oxamate and [Cu(bpca)]+ units

“…Focusing on 1H-pyrazole-based ligands, their coordination chemistry is very rich due to the possibility of coordinating to metal atoms in their neutral or deprotonated form since its NH group can be easily deprotonated in the presence of transition metal ions and a base (apparent pK a = 19,8 for 1Hpyrazole in DMSO). The pyrazolate anion acts as a bismonodentate kN:kN′ ligand, forming di-, [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] tri-, [22][23][24][37][38][39][40][41][42][43][44][45][46][47] tetra- 22,[48][49][50][51][52][53][54] and polymetallic synthons [55][56][57][58][59][60] or even coordination polymers. [61][62]…”

“…Focusing on 1 H -pyrazole-based ligands, their coordination chemistry is very rich due to the possibility of coordinating to metal atoms in their neutral or deprotonated form since its NH group can be easily deprotonated in the presence of transition metal ions and a base (apparent p K a = 19,8 for 1 H -pyrazole in DMSO). The pyrazolate anion acts as a bis-monodentate kN:kN′ ligand, forming di-, 22–38 tri-, 22–24,37–47 tetra- 22,48–54 and polymetallic synthons 55–60 or even coordination polymers. 61–64 Relatively strong magnetic interactions between paramagnetic centers such as Cu II , Co II , and Fe II can be mediated through this coordination mode.…”

Emissive silver(i) cyclic trinuclear complexes with aromatic amine donor pyrazolate derivatives: way to efficiency

“…16 Complexation of trinuclear pyrazolates with N-or P-donor ligands leads to the formation of heteroleptic metal complexes, the structures of which depend on reagent ratios. [17][18][19][20][21] Thus, different ratios of tertiary phosphine (PR 3 ) or diimine (N^N) ligands lead to mono-, di-and tetranuclear complexes. The substituents at the pyrazolate ligand also allow changing the structures.…”