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Equiatomic transition metal (T) silicides TT′Si: systematics of 29Si NMR Knight shifts

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Published/Copyright: January 13, 2025
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 79 Issue 12

Abstract

A series of 64 ternary equiatomic tetrelides TT′Tt (T = electron-poor transition metal; T′ = electron-rich transition metal; Tt = Si, Ge) was synthesized by arc-melting and subsequent annealing. The samples were characterized by powder X-ray diffraction and 20 structures were refined from single-crystal X-ray diffractometer data. These tetrelides (mostly silicides) crystallize with TiNiSi-related structures, orthorhombic space groups Pnma. They are ternary ordered, orthorhombically distorted superstructure variants of the aristotype AlB2. The precise single-crystal data show distinct differences in the bond lengths and angles within the three-dimensional [T′Si] networks as a consequence of different electron densities driven by the electronegativity differences. Systematic solid-state NMR-spectroscopic investigations allow observing the effect of the two transition metal atoms upon the 29Si isotropic resonance shifts. For the silicides featuring T′ elements from groups IX and X this value can be predicted from element-specific increments.

Keywords: transition metal silicides; crystal structure; solid-state NMR spectroscopy
Corresponding authors: Hellmut Eckert, Institut für Physikalische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster, Germany; and Institute of Physics in São Carlos, University of São Paulo, São Carlos, SP 13566-590, Brazil, E-mail: ; and Rainer Pöttgen, Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 30, 48149 Münster, Germany, E-mail:
Dedicated to Professor Hubert Schmidbaur on the occasion of his 90th birthday.

Acknowledgments

We thank Dipl.-Ing. U. Ch. Rodewald and Dr. R.-D. Hoffmann for the intensity data collections and Dr. F. Eustermann for the EDX analyses.

  1. Research ethics: Not applicable.

  2. Author contributions: All authors have accepted responsibility for the entire content of this submitted manuscript and approved the submission.

  3. Competing interests: The authors declare no conflicts of interest regarding this article.

  4. Research funding: This research was funded by Universität Münster.

  5. Data availability: Data is available from the corresponding authors on well-founded request.

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Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/znb-2024-0015).

Received: 2024-02-29
Accepted: 2024-05-17
Published Online: 2025-01-13
Published in Print: 2024-12-17

© 2024 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Preface
  4. Hubert Schmidbaur 90 years – an appreciation
  5. Reviews
  6. ‘Schmidbaur gold chemistry’ and beyond
  7. The ligand polyhedral model and its application to the structures and fluxional behaviour of the metal carbonyls
  8. Research Articles
  9. Equiatomic transition metal (T) silicides TT′Si: systematics of 29Si NMR Knight shifts
  10. New alkaline earth and rare earth representatives adopting the Ce2Al16Pt9-type structure
  11. Bis(2-chloroethyl)sulfane revisited: (ClH4C2)2S⋯S(C2H4Cl) dimers by S⋯S interaction in the solid state
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  20. Homo- and heteronuclear complexes derived from N-picoline-functionalized benzimidazolin-2-ylidene ligands
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  22. The hare and the hedgehog – Similar thermal expansion of argento- and aurophilic contacts for different reasons
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https://doi.org/10.1515/znb-2024-0015
Keywords for this article
transition metal silicides; crystal structure; solid-state NMR spectroscopy

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Preface
  4. Hubert Schmidbaur 90 years – an appreciation
  5. Reviews
  6. ‘Schmidbaur gold chemistry’ and beyond
  7. The ligand polyhedral model and its application to the structures and fluxional behaviour of the metal carbonyls
  8. Research Articles
  9. Equiatomic transition metal (T) silicides TT′Si: systematics of 29Si NMR Knight shifts
  10. New alkaline earth and rare earth representatives adopting the Ce2Al16Pt9-type structure
  11. Bis(2-chloroethyl)sulfane revisited: (ClH4C2)2S⋯S(C2H4Cl) dimers by S⋯S interaction in the solid state
  12. Structural studies of (2R,3R)-(+)-bis(diphenylphosphino)butane and (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl
  13. High-pressure synthesis and crystal structure of Al3BO6
  14. LiEu[BO3]: a lithium europium(II) ortho-oxoborate with a familiar crystal structure
  15. Fluorescence analysis of wood chips and their constituents
  16. C–S–H–PCE nanocomposites as hydration accelerator in calcined clay-limestone-blended low carbon cement
  17. An intermolecular Lewis pair based on tin acid and phosphonium ylide base functions
  18. Cyanopyridine adducts of SiF4 and SiCl4
  19. A [Zn4O(fcCO2)6] oxocarboxylate cluster: synthesis, chemical and physical properties
  20. Homo- and heteronuclear complexes derived from N-picoline-functionalized benzimidazolin-2-ylidene ligands
  21. “Coordination caps” of graded electron-donor capacity
  22. The hare and the hedgehog – Similar thermal expansion of argento- and aurophilic contacts for different reasons
  23. Atomic migration and phase transformation processes in dental amalgams over 27 years, monitored by X-ray spectroscopy and X-ray powder diffraction
  24. Book Review
  25. Hubert Schmidbaur: From Chemical Craftsmanship to the Art of Gilding Atoms. (Lives in Chemistry.)
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