Assembly of Mixed-Metal Cages Using Polyimido Antimony(III) Anions. Syntheses and Structures of [Sb3(NCy)4(HNCy)2]K·2(toluene), [Sb2(NCy)4]2M4 (M = Cu, Ag), and [Sb-(NCy)3]2Pb3 (Cy = Cyclohexyl, C6H11)

Michael A. Beswick, Natalie L. Cromhout, Christopher N. Harmer, Michael A. Paver, Paul R. Raithby, Moira Ann Rennie, Alexander Steiner, Dominic S. Wright

Research output: Contribution to journalArticlepeer-review

Abstract

Transmetalation reactions of the polyimido Sb(III) anions [Sb3(NCy)4(HNCy)2]-, [Sb2(NCy)4]2-, and [Sb(NCy)3]3- with metal sources allows the logical assembly of cage compounds containing various mixed-metal stoichiometries. The breadth of this approach is illustrated by the syntheses of [Sb(NCy)4(HNCy)2]K·2(toluene) (1), containing an early main group metal, [Sb2(NCy)4]2M4 (M = Cu (2), Ag (3)), containing transition metals, and [Sb(NCy)3Pb3] (4), containing a p-block metal. The low-temperature X-ray structures of complexes 1-4 have been determined. Crystal data: 1, monoclinic, space group C2/c, a = 18.418(3) Å, b = 11.457(2) Å, c = 24.798(6) Å, β = 90.24-(2)°, Z = 4; 3, triclinic, space group P1, a = 11.501(2) Å, b = 13.752(3) Å, c = 22.868(5) Å, α = 103.50(3)°, β = 95.89(3)°, γ = 96.71(3)°, Z = 2; 4, triclinic, space group P1, a = 11.071(2) Å, b = 14.892(2) Å, c = 17.262(2) Å, α = 65.36(3)°, β = 74.21(3)°, γ = 70.70(3)°, Z = 2. The structure of 2 has been reported in preliminary form. The K+ ion of 1 is coordinated by four of the N centers of the [Sb3(NCy)4(HNCy)2]- ligand. In addition, β-C(-H)⋯K interactions involving four of the Cy groups and MeC(-H)⋯K interactions involving two toluene molecules give the K+ ion a 10-coordinate geometry. In 2 and 3, the N centers of two [Sb2(NCy)4]2- dianions symmetrically coordinate a central M4 square-planar core. The symmetrical complexation of three Pb-(II) centers by two [Sb(NCy)3]3- trianions produces an 11-membered polyhedral cage structure in 4.

Original languageEnglish
Pages (from-to)1740-1744
Number of pages5
JournalInorganic Chemistry
Volume36
Issue number9
DOIs
Publication statusPublished - 23 Apr 1997

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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