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Synthesis and characterisation of the ternary intermetalloid clusters {M@[As(ZnMes)]} (M = Nb, Ta) from binary [M@As] precursors.

Chem Sci

June 2022

State Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab of Rare Earth Materials and Applications, School of Materials Science and Engineering, Nankai University Tianjin 300350 China

The development of rational synthetic routes to inorganic arsenide compounds is an important goal because these materials are finding applications in many areas of materials science. In this paper, we show that the binary crown clusters [M@As] (M = Nb, Ta) can be used as synthetic precursors which, when combined with ZnMes, generate ternary intermetalloid clusters with 12-vertex cages, {M@[As(ZnMes)]} (M = Nb, Ta). Structural studies are complemented by mass spectrometry and an analysis of the electronic structure using DFT.

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Endohedral clusters count as molecular models for intermetallic compounds-a class of compounds in which bonding principles are scarcely understood. Herein we report soluble cluster anions with the highest charges on a single cluster to date. The clusters reflect the close analogy between intermetalloid clusters and corresponding coordination polyhedra in intermetallic compounds.

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[Co@Sn Sb ] : An Off-Center Endohedral 12-Vertex Cluster.

Angew Chem Int Ed Engl

November 2018

Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043, Marburg, Germany.

We report on the asymmetric occupation of a 12-vertex cluster centered by a single metal atom. Three salts of related intermetalloid cluster anions, [Co@Sn Sb ] (1), [Co @Sn Sb ] (2), and [Ni @Sn Sb ] (3) were synthesized, which have pseudo-C -symmetric or pseudo-D -symmetric 12-vertex Sn/Sb shells and interstitial Co ions or Ni atoms. Anion 1 is a very unusual single-metal-"centered" 12-atom cluster, with the inner atom being clearly offset from the cluster center for energetic reasons.

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Ionic-radius-driven selection of the main-group-metal cage for intermetalloid clusters [Ln@Pbx Bi14-x](q-) and [Ln@Pby Bi13-y](q-) (x/q=7/4, 6/3; y/q=4/4, 3/3).

Chemistry

January 2015

Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg (Germany), Fax: (+49) 6421-282-5653.

Reactions of the binary, pseudo-homoatomic Zintl anion (Pb2 Bi2 )(2-) with Ln(C5 Me4 H)3 (Ln=La, Ce, Nd, Gd, Sm, Tb) in the presence of [2.2.2]crypt in ethane-1,2-diamine/toluene yielded ten [K([2.

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Origin and location of electrons and protons during the formation of intermetalloid clusters [Sm@Ga(3-x)H(3-2x)Bi(10+x)](3-) (x = 0, 1).

Angew Chem Int Ed Engl

October 2014

Fachbereich Chemie und Wissenschaftliches Zentrum für Materialwissenschaften, Philipps-Universität Marburg, Hans-Meerwein-Strasse, 35032 Marburg (Germany).

Reaction of [GaBi3](2-) with [Sm(C5Me4H)3] yielded the first protonated ternary intermetalloid clusters [Sm@Ga(3-x)H(3-2x)Bi(10+x)](3-) (1; x = 0,1). The presence of the Ga-H bonds and the transfer of electrons and protons during the formation of 1 were elucidated by a combination of experimental and quantum chemical methods, thereby rationalizing the role of the solvent ethane-1,2-diamine as a Brønsted acid. As an organic by-product, we observed the previously unknown octamethylfulvene (2) upon C-C coupling of (C5Me4H)(-).

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