Two new high-nuclearity copper(II) chloride oligomers with herringbone stacking patterns synthesized by in situ templation

Abstract

The use of trichloroiminophosphoranes Cl3P=NR to control the concurrent release of the templating cation [RNH3]+ and chloride ligand via in situ P—N and P—Cl bond cleavage produced two new copper(II) chloride oligomers. The nature of the organic substituent R was a factor in determining the chain lengths. For n-propyltrichloroiminophosphorane, the hexanuclear cluster [n-PrNH3]2[Cu6Cl14] (1) was obtained, while p-tolyltrichloroiminophosphorane generated the tetranuclear copper chloride salt [4-CH3C6H4NH3][2-Cl-4-CH3C6H3NH3][Cu4Cl10] (2). In both structures a two-dimensional framework displaying a herringbone arrangement is created by Cu—Cl secondary bonding interactions. The direct addition of the [n-PrNH3]+ cation to a CuCl2·2H2O solution under the same reaction conditions produced [n-PrNH3]2[CuCl4]. Key words: copper halides, templation, oligomers, two-dimensional frameworks.

Synthesis, Spectroscopy, and Magnetic Characterization of Copper(II) and Cobalt(II) Complexes with 2-Amino-5-bromopyridine as Ligand

“…e angles N(2)-Cu-Cl(a) and N(2)a-Cu-Cl are 91.34 ( ∘ ). Four-coordinate copper(II) compounds with two different ligands are almost distorted square planar symmetry from a coupling between electronic and vibration wave factions that lower the ground-state energy [54].…”

Solvent effects on the reactions of copper chlorides with OP(NH-t-Bu)3 — Formation of the novel [Cu5Cl10]5– anion via in situ templation

“…A variety of factors including the length, structure, and conformation of the cation, as well as interactions with the counter-anions, play important roles in determining the structures and properties of the inorganic materials formed in this way (3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21). Although facile P-N bond cleavage is an impediment in the preparation of metal imidophosphates (22,23), this liability provides an opportunity to generate novel inorganic compounds by an in situ templation approach (24)(25)(26)(27). Recently, it has been demonstrated through the use of P-N compounds as sources of amines or organic ammonium cations that this strategy produces materials that are structurally different from those obtained by the direct templation method.…”

“…The application of in situ templation has also furnished novel results for copper halide systems (26,27). For example, the concurrent release of the templating cation [RNH 3 ] + and chloride ions via in situ P-N and P-Cl bond cleavage in the precursors Cl 3 P=NR results in new copper chloride complexes, which cannot be produced by direct templation (26).…”

Synthesis, spectroscopy, and magnetic characterization of copper(II) and cobalt(II) complexes with 2-amino-5-bromopyridine as ligand

“…The angles N(2)CuCla and N(2a)CuCl are 91.34°. Four coordinate cop per(II) compounds with two different ligands are al most distorted square planar symmetry from a cou pling between electronic and vibration wave factions that lower the ground state energy [53]. Crystal structure of complex I.…”