Redox reaction between main-group elements (Te, Sn, Bi) and N-Heterocyclic-carbene-derived selenium halides: A facile method for the preparation of monomeric halides

Article abstract of DOI:10.1002/ejic.201300850

The synthesis and characterization of substituted benzimidazolin-2-selones (4c-4d) and -tellone (4i) are reported. Upon reaction with halogens (I ₂, Br₂, and Cl₂), these selones and tellone yield dihaloselones/tellone (5c-5i). The reaction of dihaloselones with elemental tellurium/tin/bismuth leads to the formation of selone-coordinated monomeric tellurium tetrahalides, tellurium dibromide (8), tin tetrahalides, and bismuth triiodide adducts (7a-7g), respectively. The structures of the tellurium tetrahalide (7a, 7d, and 7g), tellurium dibromide (8), tin tetrahalide, and bismuth triiodide adducts have been established by single-crystal X-ray analysis. The bismuth triiodide adduct is the first neutral tetrameric structure with selones. The bismuth adduct has been used as a single-source precursor for the synthesis of bismuth selenide (Bi ₂Se₃) nanoparticles, which were characterized by powder XRD patterns. The TEM images show the hexagonal shape of the nanoparticles. The reaction of dihaloselones with elemental tellurium leads to the formation of selone- coordinated monomeric tellurium tetrahalides and tellurium dibromide adducts. A plausible mechanism for the formation of tellurium halide adducts is proposed. Tellurium halide adducts are probably an intermediate in the formation of cationic diselenides. Copyright

Full text of DOI:10.1002/ejic.201300850

Eur. J. Inorg. Chem. 2013 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2013 · ISSN 1099–0682
SUPPORTING INFORMATION
DOI: 10.1002/ejic.201300850
Title: Redox Reaction between Main-Group Elements (Te, Sn, Bi) and N-Heterocyclic-Carbene-Derived Selenium Halides:
A Facile Method for the Preparation of Monomeric Halides
Author(s): Sudesh T. Manjare, Sangeeta Yadav, Harkesh B. Singh,* Ray J. Butcher

Contents
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. H, C, Se, Te NMR, Mass, and CHN spectra of 4c-4i.
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13
77
125
. H, C, Se, Te NMR, Mass, and CHN spectra of 5c-5i.
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13
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125
. H, C, Se, Te NMR, Mass, and CHN spectra of 7a-7g and 8.
. Molecular structure and crystal packing diagram of 7g.
. Variable temperature NMR spectra of 7g.
. NMR spectra of 7e through the reaction between benzimidazolin-2-selenone
and tellurium tetrabromide in CDCl3.
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8
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. H, C, Se NMR, Mass, and CHN spectra of 9a-9c and 10.
. Molecular structure and crystal packing diagram of 9a.
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. H, C, Se NMR, Mass, and CHN spectra of 9b-9c and 10.
0. Tables S1 and S2

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Figure S1. H NMR spectrum of 4c in CDCl .
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Figure S2. C NMR spectrum of 4c in CDCl .

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Figure S3. Se NMR spectrum of 4c in CDCl .
Figure S4. Mass spectrum of 4c.

Figure S5. Elemental analysis of 4c.
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Figure S6. H NMR spectrum of 4d in CDCl .
3

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Figure S7. C NMR spectrum of 4d in CDCl
3
.
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Figure S8. Se NMR spectrum of 4d in CDCl
3
.

Figure S9. HRMS of 4d.
Figure S10. Elemental analysis of 4d.

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Figure S11. H NMR spectrum of 4i in CDCl
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.
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Figure S12. C NMR spectrum of 4i in CDCl
3
.

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Figure S13. Te NMR spectrum of 4i in CDCl .
Figure S14. HRMS spectrum of 4i.

Figure S15. Elemental analysis of 4i.
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Figure S16. H NMR spectrum of 5c in CDCl .
3

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Figure S17. C NMR spectrum of 5c in CDCl
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.
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Figure S18. Se NMR spectrum of 5c in CDCl
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.

Figure S19. Elemental analysis of 5c
.
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Figure S20. H NMR spectrum of 5d in CDCl .
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Figure S21. C NMR spectrum of 5d in CDCl .
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Figure S22. Se NMR spectrum of 5d in CDCl .
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Figure S23. Mass spectrum of 5d.
Figure S24. Elemental analysis of 5d

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Figure S25. H NMR spectrum of 5e in CDCl
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.
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Figure S26. C NMR spectrum of 5e in CDCl
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.

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Figure S27. Se NMR spectrum of 5e in CDCl .
Figure S28. Mass spectrum of 5e.

Figure S29. Elemental analysis of 5e
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Figure S30. H NMR spectrum of 5f in CDCl .
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Figure S31. C NMR spectrum of 5f in CDCl .
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Figure S32. Se NMR spectrum of 5f in CDCl .
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Figure S33. Mass spectrum of 5f.
Figure S34. Elemental analysis of 5f

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Figure S35. H NMR spectrum of 5g in CDCl
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.
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Figure S36. C NMR spectrum of 5g in CDCl
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.

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Figure S37. Se NMR spectrum of 5g in CDCl .
Figure S38. Mass spectrum of 5g.

Figure S39. Elemental analysis of 5g
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Figure S40. H NMR spectrum of 5h in CDCl .
3

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3
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Figure S41. C NMR spectrum of 5h in CDCl .
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7
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Figure S42. Se NMR spectrum of 5h in DMSO-d .

Figure S43. HRMS spectrum of 5h.
Figure S44. Elemental analysis of 5h

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Figure S45. H NMR spectrum of 5i in CDCl
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.
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Figure S46. C NMR spectrum of 5i in CDCl
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.

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Figure S47. Te NMR spectrum of 5i in CDCl .
Figure S48. Mass spectrum of 5i.

Figure S49. Elemental analysis of 5i.
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Figure S50. H NMR spectrum of 7a in CDCl .
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Figure S51. C NMR spectrum of 7a in CDCl
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.
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Figure S52. Se NMR spectrum of 7a in CDCl
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.

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Figure S53. Te NMR spectrum of 7a in CDCl .
Figure S54. Mass spectrum of 7a.

Figure S55. Elemental analysis of 7a.
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Figure S56. H NMR spectrum of 7b in CDCl .
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