An unusually stable octanuclear σ-mesityl-bridged µ4-oxo-copper(i) complex encapsulated by a pyrazolate-based compartmental ligand scaffold

Abstract

A new compartmental pyrazole-derived chelating ligand, four equivalents of mesitylcopper and stoichiometric amounts of dioxygen lead to the formation of a remarkably stable organometallic framework that can be described as a heteroleptic O-centered cuprate anion [(MesCu(I))(4)(mu(4)-O)](2-) linked via sigma-mesityl-bridges to two surrounding binuclear Cu(I)-pyrazolate clamps.

Remarkable Stability of Copper(II)–N-Heterocyclic Carbene Complexes Void of an Anionic Tether

“…Mass spectrometry and elemental analysis confirmed molecular formulas of [Cu-(NHC) 2 Br]PF 6 for both complexes (6b,c). Crystals suitable for X-ray diffraction analysis were obtained via the vapor diffusion of diethyl ether into a concentrated solution of the complexes in acetonitrile.…”

Structural Variations in Tetrasilver(I) Complexes of Pyrazolate-bridged Compartmental N-Heterocyclic Carbene Ligands

“…3,5-Bis(chloromethyl)-1-(tetrahydropyran-2-yl)-pyrazole [21], 3,5-bis(chloromethyl)-1-(tetrahydropyranyl-2-yl)-4-phenyl-1H-pyrazole [22] and N-substituted imidazoles [10] were prepared according to procedures found in the literature. All other chemicals were purchased and used as supplied.…”

Coordination Versatility of Pyrazole‐Based Ligands towards High‐Nuclearity Transition‐Metal and Rare‐Earth Clusters

“…Variation of the side arm chain lengths gives some control over metal-metal separation, while the number and type of side arm donor sites allow the determination of electronic and coordinative properties. An important part of this research has been developed by Meyer and co-workers, [111][112][113][114][115][116][117][118][119][120][121][122][123][124][125][126] who have studied the coordination ability of the 3,5-disubstituted pyrazole ligands with chelating side arms, mainly with N-donor atoms. [11] The main part of the review was dedicated to dinuclear compounds.…”

“…With urea as a ligand, a tetranuclear nickel(II) compound is formed, in which the presence of two low-spin nickel(II) ions and two high-spin nickel(II) ions that interact ferromagnetically is confirmed by magnetic susceptibility studies. [126] The use of more bulky pyrazole ligands (i.e. The pyrazolato ligand bridges the two metal ions, and in some cases, the dinuclear structures, [M 2 L2a] + (M = Cu II and Zn II ), are linked by carbonates incorporated from air, [111,114] µ 4 -peroxido, [122] phosphato [113] or oxazetidinylacetato ligands.…”