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SYNTHESIS AND CRYSTALLOGRAPHIC STUDIES OF CROWN THIOETHER COMPLEXES OF BISMUTH(III)
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UNSPECIFIED (1992) SYNTHESIS AND CRYSTALLOGRAPHIC STUDIES OF CROWN THIOETHER COMPLEXES OF BISMUTH(III). JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (4). pp. 591-596. ISSN 0300-9246.
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Abstract
The pale yellow bismuth(III)-crown thioether complexes BiCl3.[12]aneS4 1 and BiCl3.[15]aneS5.0.5MeCN 2 have been prepared and characterised. An X-ray crystal structure determination of 1 shows the central bismuth atom bonded to three chlorine atoms, Bi-Cl mean 2.571 angstrom, Cl-Bi-Cl 90.9(1)-94.3(1)-degrees, and all four sulfur atoms of the [12]aneS4 macrocycle, Bi-S 2.987(3)-3.206(3) angstrom, in an approximate half-sandwich structure. The four sulfur atoms are exactly coplanar and the bismuth atom sits in a central location over the ring at a distance of 1.87 angstrom from this plane. This is the first genuine example of endo complexation for [12]aneS4 involving a p-block element. Compound 1 crystallises in the monoclinic space group P2(1)/n with a = 7.985(4), b = 12.956(7), c = 15.278(9) angstrom, beta = 101.47(4)-degrees and Z = 4.2099 Observed reflections [I/sigma(I) greater-than-or-equal-to 2.0] gave in the final refinement R = 0.037. The structure of BiCl3.[15]aneS5.0.5MeCN 2 shows full co-ordination of the [15]aneS5 macrocycle to the BiCl3 unit in a half-sandwich arrangement, with two independent identical molecules, Bi-Cl mean 2.565(7) angstrom, Bi-S 3.057(7)-3.433(7) angstrom, Cl-Bi-Cl 86.5(2)-93.0(2)-degrees; acetonitrile is trapped as lattice solvate. The ligand undergoes a conformational change (exo- to endo-dentate) on complex formation. Compound 2 crystallises in the orthorhombic space group Pbca with a = 16.972(9), b = 1 5.418(8), c = 30.60(2) angstrom, and Z = 16. 2951 Observed reflections [I/sigma(I) greater-than-or-equal-to 2.0] gave in the final refinement R = 0.0545. The resulting conformations of the macrocyclic ligands are discussed in terms of gauche/anti preferences and structural comparisons are drawn between 1 and 2 and their oxocrown counterparts.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | ||||
Publisher: | ROYAL SOC CHEMISTRY | ||||
ISSN: | 0300-9246 | ||||
Official Date: | February 1992 | ||||
Dates: |
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Number: | 4 | ||||
Number of Pages: | 6 | ||||
Page Range: | pp. 591-596 | ||||
Publication Status: | Published |
Data sourced from Thomson Reuters' Web of Knowledge
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