Hexanuclear Niobium Cluster Compounds with Protonated N‐Base Cations. Issue 18 (7th May 2020)

• Record Type: Journal Article
• Authors: König, Jonas; Dartsch, Ina; Sperlich, Eric; Guillamón, Eva; Llusar, Rosa; Köckerling, Martin
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 646:Issue 18(2020)
• Page Start: 1531
• Page End: 1538
• Publication Date: 2020-05-07
• Subjects: Cluster -- Niobium -- Mass spectrometry -- X‐ray diffraction -- Hydrogen bonds; Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.202000097
• Languages: English
• ISSNs: 0044-2313

Abstract

Abstract : Octahedral clusters of the [ M 6 X12 ] type offer numerous possibilities to form structural arrangements through different choices of bonding situations. In this paper a series of new cluster compounds of the transition metal niobium is described, which consist of the [Nb6 Cl18 ] 2–, and in one case [Nb6 Cl18 ] 3–, anion and protonated N‐base cations ([MIm‐H] +, [ n Pr3 N‐H] +, [TMGu‐H] +, and [Tzn‐H] + ). They all are prepared using water scavenger compounds [SOCl2 or (Ac)2 O] under oxidising conditions, resulting in two‐electron (or one‐electron, respectively) oxidized cluster units with respect to the starting material [Nb6 Cl14 (H2 O)4 ]· 4H2 O. Of five members of this group single‐crystal X‐ray structures were determined. The cluster anions exist in all structures as discrete units. The acidic H atoms of all N‐bases are hydrogen bonded to H acceptors, in 4 cases to outer, exo bonded Cl atoms of the cluster unit and in one case to the O atom of a co‐crystallized THF molecule. In [TMGu‐H]2 [Nb6 Cl18 ] chains of cluster anions exist hydrogen‐bonded through bridging [TMGu‐H] + cations. ESI mass spectra of [MIm‐H]2 [Nb6 Cl18 ]· 2SOCl2 and [TMGu‐H]2 [Nb6 Cl18 ] show the expected isotopic distribution patterns for the anions together with other peaks associated to chloride mass losses and/or reduction processes. Abstract :