Hydrocarbon-Soluble Mercuracarborands: Syntheses, Halide Complexes, and Supramolecular Chemistry

Zhiping Zheng, Carolyn B. Knobler, Mark D. Mortimer, Gapgoung Kong, M. Frederick Hawthorne

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Abstract

The syntheses of macrocyclic species composed of carborane derivatives joined via their carbon vertices by electrophilic mercury atoms are described. The reaction of closo-1,2-Li2[C2B10H10-xR x] with HgI2 gives Li2[(1,2-C2B10H10-xR xHg)42] [R = Et, x = 2 (5·I2Li2); R = Me, x = 2 (6·I2Li2); R = Me, x = 4 (7·I2Li2)]. 6·I2(K·[18]-dibenzocrown-6)2 crystallizes in the monoclinic space group C2/m [a = 28.99(2) Å, b = 18.19(1) Å, c = 13.61(1) Å, β= 113.74(2)°, V = 6568 Å3, Z = 4, R = 0.060, Rw = 0.070]; 7-I2(NBu4)2 crystallizes in the monoclinic space group P21/c [a = 12.77(1) Å, b = 21.12(2) Å, c = 20.96(2) Å, β = 97.87(2)°, V = 5600 Å3, Z = 2, R = 0.072, Rw = 0.082]. The precursor to 7, closo-8,9,10,12-Me4-l,2-C2B10H8 (4), is made in a single step by reaction of closo-1,2-C2B10H12 with Mel in trifluoromethanesulfonic acid. The free hosts 5, 6, and 7 are obtained by reaction of the iodide complexes with stoichiometric quantities of AgOAc. A 199Hg NMR study indicates that sequential removal of iodide from 5·I2Li2 and 6·I2Li2 with aliquots of AgOAc solution leads to formation of two intermediate host-guest complexes in solution, presumed to be 5(6)ILi and 52(6)2·ILi. Crystals grown from a solution of 6·I2Li2 to which 1 equiv of AgOAc solution had been added proved to be an unusual stack structure with the formula 63·I4Li4 [tetragonal, I4/m, a = 21.589(2) Å, c = 21.666(2) Å, V= 10098 Å3, Z = 2, R = 0.058, Åw = 0.084]. Addition of 2 equiv of NBu4Br ion to 5 or 6 gives 5·Br2(NBu4)2 and 6·Br2(NBu4)2, respectively, while addition of 1 equiv of KBr to 6 forms 6·lBrK. 5·Br2(NBu4)2 crystallizes in the triclinic space group P1̄, [a = 10.433(1) Å, b= 13.013(1) Å, c= 15.867(2) Å, α = 91.638(2)°, β = 97.186(3)°, γ = 114.202(2)°, V= 1492 Å3, Z = 1, R = 0.078, Rw = 0.104]. The hosts 5 and 6 form 1:1 supramolecular adducts with the polyhedral anions B10I102- and B12I122- in solution.

Original languageEnglish (US)
Pages (from-to)1235-1243
Number of pages9
JournalInorganic Chemistry
Volume35
Issue number5
Publication statusPublished - 1996
Externally publishedYes

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ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Zheng, Z., Knobler, C. B., Mortimer, M. D., Kong, G., & Frederick Hawthorne, M. (1996). Hydrocarbon-Soluble Mercuracarborands: Syntheses, Halide Complexes, and Supramolecular Chemistry. Inorganic Chemistry, 35(5), 1235-1243.