Air‐Stable, Well‐Soluble A^I₂[Nb₆Cl₁₈] Cluster Compounds (A^I = Organic Cation): A New Route for Preparation, Single‐Crystal Structures, Properties, and ESI‐Mass Spectra

Abstract

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A Hexanuclear Niobium Cluster Compound Crystallizing as Macroscopic Tubes

“…That of the exo ‐directed Cl3 atom is found at 2.4779(9) Å. These values are in accordance with an two‐electron oxidized cluster unit bearing 14 cluster‐based electrons …”

“…All the water ligands of the starting material are replaced by chloride ions and the co‐crystallized H 2 O molecules removed. A two‐electron oxidation of the cluster unit happens, as summarized in Scheme …”

“…All the water ligands of the startingm ateriala re replaced by chloride ions and the co-crystallized H 2 Om olecules removed.Atwoelectron oxidation of the cluster unit happens,a ss ummarized in Scheme 1. [8] If the diethyl ether is introduced slowly by ad iffusion process into the cluster solutioni nS OCl 2 ,a so utlined in the Exper-imentalS ection, large, macroscopic, hexagonal tubes grow on the glass surface of the vials. In the earlier reactiona ttempts 18-crown-6 wasp resent in the reaction mixture.…”

“…[9] In accordance with the " 3s ymmetry the Nb atoms within the two triangularp lanes of the trigonal antiprism with the same z coordinates are equilateral with aN b ÀNb distance of 3.0151(5) , whereas the distance between the Nb atomsb etween the two triangles is slightly longer, 3.0356 (5) .T he NbÀCl distances of the edge-bridging halides Cl1 and Cl2 measurei na verage 2.4217 .T hat of the exo-directed Cl3 atom is found at 2.4779(9) .T hese values are in accordance with an two-electron oxidized clusteru nit bearing 14 cluster-based electrons. [8] The diethylo xonium-diethyl etherate cation is located aroundt he Wyckoff site 2d with threefold rotational symmetry. Because the [(Et 2 O) 2 H + ]c ation does not have this point symmetry it is disordered aroundt his special positiona nd refined using as plit modelw ith a1 /3 occupation of each part.…”

New Hexanuclear Niobium Cluster Compounds with Perfluorinated Ligands Made Using Ionic Liquids

“…The inner ligands of the [ M 6 X i 12 ] type bridge all the edges of the metal atom octahedron (μ). A rich chemistry of hexanuclear clusters has been developed, based on a large choice of different outer ligands, ranging from halogenido, organic anions, neutral molecules, to organic cations . The cluster units are stable with different numbers of cluster based electrons (CBE's, which are 16, 15, or 14 for hexanuclear group VB transition metal clusters), going along with different oxidation numbers.…”