Startseite A new aspect of the “pseudo water” concept of bis(trimethylsilyl)carbodiimide – “pseudohydrates” of aluminum
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A new aspect of the “pseudo water” concept of bis(trimethylsilyl)carbodiimide – “pseudohydrates” of aluminum

  • Katrin Krupinski , Erica Brendler , Robert Gericke , Jörg Wagler und Edwin Kroke ORCID logo EMAIL logo
Veröffentlicht/Copyright: 29. September 2018
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Zeitschrift für Naturforschung B
Aus der Zeitschrift Zeitschrift für Naturforschung B Band 73 Heft 11

Abstract

Bis(trimethylsilyl)carbodiimide (BTSC), so-called “pseudo water” because of some analogies such as similar (group)electronegativities of Me3Si– vs. H– and –N=C=N– vs. –O–, may form two different kinds of “pseudo hydrates” of metals (M), i.e. M–N(SiMe3)=C=N(SiMe3) and M–N≡C–N(SiMe3)2, derived from its carbodiimide and cyanamide isomeric forms, respectively. With anhydrous AlCl3 in Me3SiCl solution BTSC was shown to be capable of forming both kinds of solvates, i.e. Cl3Al–N(SiMe3)–C≡N(SiMe3) (1) and ((Cl3Al)(Me3Si)NCN)3–Al–(N≡C–N(SiMe3)2)3 (2). Both compounds were isolated as crystalline solids, which undergo condensation reactions upon storage. By single-crystal X-ray diffraction analysis the constitution of 1 was confirmed unambiguously, and quantum chemical calculations (B3LYP/6-311++g(d,p)) confirmed that compound 1 is 6 kcal mol−1 more stable than its hypothetical N,N-bis(trimethylsilyl)cyanamide isomer Cl3Al–N≡C–N(SiMe3)2. Compound 1 represents the first crystallographically confirmed disilylcarbodiimide complex of a metal salt. The molecules of compound 2 are heavily disordered in the solid state (positional disorder of N≡C–N(SiMe3)2 vs. N≡C–N(SiMe3)(AlCl3) and positional disorder of SiMe3 vs. AlCl3 groups in the latter). Therefore, the identity of 2 was additionally confirmed by 13C, 15N, 27Al and 29Si CP/MAS NMR spectroscopy.

Keywords: aluminum chloride coordination; carbodiimide; cyanamide; isomerism; solid-state NMR; X-ray diffraction

Dedicated to: Professor Werner Uhl on the occasion of his 65th birthday.

Acknowledgements

The German research foundation (DFG, Bonn) is gratefully acknowledged for financial support (project number: KR1739/18-1).

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/znb-2018-0137).

Received: 2018-06-30
Accepted: 2018-09-01
Published Online: 2018-09-29
Published in Print: 2018-11-27

©2018 Walter de Gruyter GmbH, Berlin/Boston

Artikel in diesem Heft

  1. Frontmatter
  2. In this Issue
  3. Preface
  4. Congratulations to Bernt Krebs
  5. Structural and IR-spectroscopic characterization of pyridinium acesulfamate, a monoclinic twin
  6. Cationic tri(ferrocenecarbonitrile)silver(I)
  7. Ternary indides RE3T2In4 (RE=Dy–Tm; T=Pd, Ir)
  8. Mixing SbIII and GeIV occupancy in the polyoxovanadate {V14E8} archetype
  9. Biolabeling with cobaltocinium tags
  10. Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes in solution and in the solid state
  11. Hydrothermal synthesis and structure determination of a new calcium iron ruthenium hydrogarnet
  12. 7-Methyl-6-furylpurine forms dinuclear metal complexes with N3,N9 coordination
  13. Structural and magnetic investigations of the pseudo-ternary RE2TAl3 series (RE=Sc, Y, La–Nd, Sm, Gd–Lu; T=Ru, Rh, Ir) – size dependent formation of two different structure types
  14. A new stacking variant of Na2Pt(OH)6
  15. Alkali chalcogenido ortho manganates(II) A6MnQ4 (A=Rb, Cs; Q=S, Se, Te)
  16. Studie über den Einfluss des Fluorierungsgrades an einem tetradentaten C^N*N^C-Luminophor auf die photophysikalischen Eigenschaften seiner Platin(II)-Komplexe und deren Aggregation
  17. Hydrothermal growth mechanism of SnO2 nanorods in aqueous HCl
  18. Preface
  19. Congratulations to Werner Uhl
  20. The stannides REIr2Sn4 (RE=La, Ce, Pr, Nd, Sm)
  21. 1H-[1,2,4]Triazolo[4,3-a]pyridin-4-ium and 3H-[1,2,4]triazolo[4,3-a]quinolin-10-ium derivatives as new intercalating agents for DNA
  22. Functionalization of 1,3-diphosphacyclobutadiene cobalt complexes via Si–P bond insertion
  23. A new aspect of the “pseudo water” concept of bis(trimethylsilyl)carbodiimide – “pseudohydrates” of aluminum
  24. (NH4)InB8O14 – a high-pressure borate combining BO3 groups with corner- and edge-sharing BO4 tetrahedra
  25. Two series of rare earth metal-rich ternary aluminium transition metallides – RE6Co2Al (RE=Sc, Y, Nd, Sm, Gd–Tm, Lu) and RE6Ni2.25Al0.75 (RE=Y, Gd–Tm, Lu)
  26. Alkylaluminum, -gallium, -magnesium, and -zinc monophenolates with bulky substituents
  27. Note
  28. Synthesis and crystal structure of the copper silylamide cluster compound [Cu9{MesSi(NPh)3}2 (PhCO2)3]
https://doi.org/10.1515/znb-2018-0137
Schlagwörter für diesen Artikel
aluminum chloride coordination; carbodiimide; cyanamide; isomerism; solid-state NMR; X-ray diffraction

Artikel in diesem Heft

  1. Frontmatter
  2. In this Issue
  3. Preface
  4. Congratulations to Bernt Krebs
  5. Structural and IR-spectroscopic characterization of pyridinium acesulfamate, a monoclinic twin
  6. Cationic tri(ferrocenecarbonitrile)silver(I)
  7. Ternary indides RE3T2In4 (RE=Dy–Tm; T=Pd, Ir)
  8. Mixing SbIII and GeIV occupancy in the polyoxovanadate {V14E8} archetype
  9. Biolabeling with cobaltocinium tags
  10. Formation of di- and polynuclear Mn(II) thiocyanate pyrazole complexes in solution and in the solid state
  11. Hydrothermal synthesis and structure determination of a new calcium iron ruthenium hydrogarnet
  12. 7-Methyl-6-furylpurine forms dinuclear metal complexes with N3,N9 coordination
  13. Structural and magnetic investigations of the pseudo-ternary RE2TAl3 series (RE=Sc, Y, La–Nd, Sm, Gd–Lu; T=Ru, Rh, Ir) – size dependent formation of two different structure types
  14. A new stacking variant of Na2Pt(OH)6
  15. Alkali chalcogenido ortho manganates(II) A6MnQ4 (A=Rb, Cs; Q=S, Se, Te)
  16. Studie über den Einfluss des Fluorierungsgrades an einem tetradentaten C^N*N^C-Luminophor auf die photophysikalischen Eigenschaften seiner Platin(II)-Komplexe und deren Aggregation
  17. Hydrothermal growth mechanism of SnO2 nanorods in aqueous HCl
  18. Preface
  19. Congratulations to Werner Uhl
  20. The stannides REIr2Sn4 (RE=La, Ce, Pr, Nd, Sm)
  21. 1H-[1,2,4]Triazolo[4,3-a]pyridin-4-ium and 3H-[1,2,4]triazolo[4,3-a]quinolin-10-ium derivatives as new intercalating agents for DNA
  22. Functionalization of 1,3-diphosphacyclobutadiene cobalt complexes via Si–P bond insertion
  23. A new aspect of the “pseudo water” concept of bis(trimethylsilyl)carbodiimide – “pseudohydrates” of aluminum
  24. (NH4)InB8O14 – a high-pressure borate combining BO3 groups with corner- and edge-sharing BO4 tetrahedra
  25. Two series of rare earth metal-rich ternary aluminium transition metallides – RE6Co2Al (RE=Sc, Y, Nd, Sm, Gd–Tm, Lu) and RE6Ni2.25Al0.75 (RE=Y, Gd–Tm, Lu)
  26. Alkylaluminum, -gallium, -magnesium, and -zinc monophenolates with bulky substituents
  27. Note
  28. Synthesis and crystal structure of the copper silylamide cluster compound [Cu9{MesSi(NPh)3}2 (PhCO2)3]
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