77Se solid-state NMR studies of [M(Se4)2]2- anions (M = Zn, Cd, Hg)

Patrick J. Barrie, Robin J H Clark, Robert Withnall, Duck Young Chung, Kang Woo Kim, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

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Abstract

77Se solid-state NMR spectra have been recorded with cross-polarization and magic-angle spinning on [M(Se4)2]2- complexes with [Me4N]+ (M = Zn, Cd, Hg) and [Et4N]+ (M = Cd, Hg). The large chemical shift anisotropies (of the order of 1000 ppm) mean that fast spinning speeds (9-11 kHz) are needed in order to reveal the number of crystallographic selenium sites present within the solid. The spectra enable the principal components of the 77Se shielding tensor to be calculated from the spinning sideband intensities. Differences between the 77Se isotropic chemical shifts observed for the [Et4N]+ complexes and for the [Me4N]+ complexes reflect small structural changes in the [M(Se4)2]2- geometry with cation. J-coupling to 199Hg and 111/113Cd are also observed. The solid-state NMR results are compared with similar work in solution. A single-crystal X-ray structure determination of [Me4N]2-[Hg(Se4)2]·0.5DMF is reported (monoclinic crystal system, space group C2/c). The Hg atom is tetrahedrally coordinated by two chelating tetraselenide ligands with both HgSe4 rings adopting the envelope conformation. The FT Raman spectrum of [Me4N]2[Cd(Se4)2] is also reported.

Original languageEnglish
Pages (from-to)1212-1216
Number of pages5
JournalInorganic Chemistry
Volume33
Issue number6
Publication statusPublished - 1994

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metal spinning
Anions
Nuclear magnetic resonance
Chemical shift
anions
solid state
nuclear magnetic resonance
chemical equilibrium
Magic angle spinning
cross polarization
Selenium
Chelation
selenium
sidebands
Shielding
Tensors
shielding
Conformations
Cations
Raman scattering

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Barrie, P. J., Clark, R. J. H., Withnall, R., Chung, D. Y., Kim, K. W., & Kanatzidis, M. G. (1994). 77Se solid-state NMR studies of [M(Se4)2]2- anions (M = Zn, Cd, Hg). Inorganic Chemistry, 33(6), 1212-1216.

77Se solid-state NMR studies of [M(Se4)2]2- anions (M = Zn, Cd, Hg). / Barrie, Patrick J.; Clark, Robin J H; Withnall, Robert; Chung, Duck Young; Kim, Kang Woo; Kanatzidis, Mercouri G.

In: Inorganic Chemistry, Vol. 33, No. 6, 1994, p. 1212-1216.

Research output: Contribution to journalArticle

Barrie, PJ, Clark, RJH, Withnall, R, Chung, DY, Kim, KW & Kanatzidis, MG 1994, '77Se solid-state NMR studies of [M(Se4)2]2- anions (M = Zn, Cd, Hg)', Inorganic Chemistry, vol. 33, no. 6, pp. 1212-1216.
Barrie PJ, Clark RJH, Withnall R, Chung DY, Kim KW, Kanatzidis MG. 77Se solid-state NMR studies of [M(Se4)2]2- anions (M = Zn, Cd, Hg). Inorganic Chemistry. 1994;33(6):1212-1216.
Barrie, Patrick J. ; Clark, Robin J H ; Withnall, Robert ; Chung, Duck Young ; Kim, Kang Woo ; Kanatzidis, Mercouri G. / 77Se solid-state NMR studies of [M(Se4)2]2- anions (M = Zn, Cd, Hg). In: Inorganic Chemistry. 1994 ; Vol. 33, No. 6. pp. 1212-1216.
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AB - 77Se solid-state NMR spectra have been recorded with cross-polarization and magic-angle spinning on [M(Se4)2]2- complexes with [Me4N]+ (M = Zn, Cd, Hg) and [Et4N]+ (M = Cd, Hg). The large chemical shift anisotropies (of the order of 1000 ppm) mean that fast spinning speeds (9-11 kHz) are needed in order to reveal the number of crystallographic selenium sites present within the solid. The spectra enable the principal components of the 77Se shielding tensor to be calculated from the spinning sideband intensities. Differences between the 77Se isotropic chemical shifts observed for the [Et4N]+ complexes and for the [Me4N]+ complexes reflect small structural changes in the [M(Se4)2]2- geometry with cation. J-coupling to 199Hg and 111/113Cd are also observed. The solid-state NMR results are compared with similar work in solution. A single-crystal X-ray structure determination of [Me4N]2-[Hg(Se4)2]·0.5DMF is reported (monoclinic crystal system, space group C2/c). The Hg atom is tetrahedrally coordinated by two chelating tetraselenide ligands with both HgSe4 rings adopting the envelope conformation. The FT Raman spectrum of [Me4N]2[Cd(Se4)2] is also reported.

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