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The Basicity of Silylamines and Alkylamines: An Equilibrium Study of the Competitive Borane Adduct Formation

  • Gerald Huber and Hubert Schmidbaur
Published/Copyright: June 2, 2014
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Zeitschrift für Naturforschung B
From the journal Zeitschrift für Naturforschung B Volume 53 Issue 10

Abstract

In order to investigate the Lewis acid/base chemistry of silylamines in solution, the equilibrium reactions of Me3SiNMe2 / Me3SiNMe2(BH3) and different amines NR3 / amineboranes NR3(BH3) were monitored by 1H NMR spectroscopy in C6D6 and CDCI3 at 60 °C. For the equilibrium of the reference silylamine/-borane and Me3CNMe2 / Me3CNMe2(BH3) values K = 0.35 (AG = 3.1 kJ mol-1) in C6D6 and K = 0.50 (AG = 2.0 kJ mol-1) in CDCl3 have been estimated, showing that both the silylamine and the C/Si-analogous organic amine have very similar donor properties. Small amines like NMe3 proved to be much more powerful donors than the silylamine Me3SiNMe2, whereas bulky amines are less efficient donors, indicating that steric effects play an important role. The formation of BH3 adducts of Me2NSiH3 and (H3Si)3N which could not be followed experimentally owing to the low stability of the products, has been studied by quantum chemical calculations. A comparison with data for Me3N(BH3) shows that the silylamines are poorer donors, but the reason for this remains unclear

Keywords: Silylamines; Alkylamines; Borane Adducts; Amineboranes; Basicity Studies
Received: 1998-7-21
Published Online: 2014-6-2
Published in Print: 1998-10-1

© 1946 – 2014: Verlag der Zeitschrift für Naturforschung

Articles in the same Issue

  1. Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LIX [1], Ein Addukt des Me3P-substituierten Ferrio-diphenylphosphans Cp(OC)(Me3P)Fe-PPh2 mit Methylisothiocyanat: Darstellung, Protonierung und Methylierung / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LIX [1]. An Adduct of the Me3P-Substituted Ferrio-diphenylphosphane Cp(OC)(Me3P)Fe-PPh2 and Methylisothiocyanate: Synthesis, Protonation, and Methylation
  2. Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LX [1]. Ferrio-(thiocarbamoyl)phosphane Cp(OC)2 Fe-P(Mes)[C(=S)-N(R)H] (R = Me, Et, f-Bu): Aufbau aus dem Ferrio-mesitylphosphan Cp(OC)2 Fe-P(Mes)H und Organoisothiocyanaten sowie Quaternisierung mit Alkylhalogeniden und Oxidation mit Schwefel / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LX [1]. Ferrio-(thiocarbamoyl)phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R= Me, Et, r-Bu): Build-up from the Ferrio-mesitylphosphane Cp(OC)2Fe-P(Mes)H and Organoisothiocyanates, Quatemization with Alkyl Halides and Oxidation with Sulfur
  3. Phosphenium-Komplexe, 43 [1]. Ringöffnungsreaktionen der dreigliedrigen Phosphametallacyclen {PR2 = P(o-Tol)2, P(Ph)(o-Tol), P(Mes)[C(S)N(H)Et], P(/-Bu)[C(O)N(H)Et} / Phosphenium Complexes, 43 [1]. Ring-Opening Reactions of the Three-Membered Phosphametallacycles {PR1 = P(o-Tol)2, P(Ph)(oTol), P(Mes)[C(S)N(H)Et], P(r-Bu)[C(0)N(H)Et}
  4. Magnesium Bis[D(-)-Mandelate] Dihydrate and Other Alkaline Earth, Alkali, and Zinc Salts of Mandelic Acid
  5. The Basicity of Silylamines and Alkylamines: An Equilibrium Study of the Competitive Borane Adduct Formation
  6. Kristallchemische Beziehungen von CO6O2 [TeO4 (CoAsO5)2] zur Steinsalzstruktur von CoO mit einem Beitrag über magnetische Messungen an CO6O2[TeO4(CoAsO5)2] / Crystal Chemical Relations of Co6O2[TeO4(CoAsO5)2] to the Rocksalt Structure of CoO and a Contribution on Magnetic Measurements of Co6O2[TeO4(CoAsO5)2]
  7. Synthese, Kristallstruktur und Eigenschaften von Triguanidinium-tri--imidocyclotriphosphat-Monohydrat und Tetraguanidinium-tetra-/i-imidocyclotetraphosphat-Tetrahydrat, [C(NH2)3]3(PO2NH)3 · H2O und [C(NH2)3]4(PO2NH)4 · 4 H2O / Synthesis, Crystal Structure, and Properties of Triguanidinium Tri-/i-imidocyclotriphosphate Monohydrate and Tetraguanidinium Tetra-/i-imidocyclotetraphosphate Tetrahydrate, [C(NH2)3]3(PO2NH)3 · H2O and [C(NH2)3]4(PO*NH)4 · 4 H2O
  8. Untersuchungen an Polyhalogeniden, XXXVII [1]. Heptaiodide(3-) von Amminkomplexen des Chroms und Cobalts: Hexamminchrom(III)heptaiodid [Cr(NH3)6](I3)(I4) und die Tri-μ-hydroxo-bis[metall(III)-triammin]heptaiodide [(NH3)3 M(OH)3M(NH3)3](I3)2I mit M = Co, Cr / Studies o f Polyhalides, XXXVII [1]. Heptaiodides(3-) of Ammine Complexes of Chromium and Cobalt: Hexamminechromium(III) heptaiodide [Cr(NH3)6](I3)(I4) and the Tri-μ-hydroxo-bis[metal(III)-triammine] heptaiodides [(NH3)3M(OH)3M(NH3)3](I3)2I with M = Co, Cr
  9. Functionalized 1,1-Ethene Dithiolates as Ligands, V [1]. Synthesis and Crystal Structure of Palladium(II) and Platinum(II) Complexes with Dithioylidene Barbituric Acid Ligands. Molecular Structure of a 2,6-Diaminopyridine-Platinum(II) Barbiturate Complex
  10. Solvothermal Synthesis and Crystal Structure Determination of Tris- (ethyleneamine-ammonium) Tetraselenoantimonat: Non-Centrosymmetry Mediated by an Extended Unusual N-H···N Hydrogen Bonded Network?
  11. Thermische Zersetzung und Lösungskalorimetrie von Ammoniumeuropiumchloriden / Thermal Decomposition and Solution Calorimetry of Ammonium Europium Chlorides
  12. Photochemical Reductive Elimination of Nitrogen from Triazidogallium(III). Generation of Luminescent Gallium(I)
  13. Zur Existenz von [ReNCl4-nFn]- (n = 1-3) Nitridorhenat(VI)-Gemischt- ligandkomplexen -Eine EPR-Untersuchung / EPR Evidence of [ReNCl4-n FnJ– (n = 1-3) Nitridorhenate(VI) Mixed-Ligand Complexes
  14. Synthesis and Crystal Structure of N-[(15,4R)-2-Oxo-pinanyl]-β-alanine Methylester
  15. Synthesis and Conformation of Nucleoside 5'-S-Thiosulfates
  16. Niedere Hydrate aliphatischer primärer Amine. Neue Untersuchungen zu Bildung und Struktur [1] / Lower Hydrates of Aliphatic Primary Amines. New Studies of Formation and Structure [1]
  17. Synthesis and Dimroth Rearrangement of 6-Cyano-l,2,4-triazolo- [4,3-a]pyrimidin-5- and 7-ones. A Novel Alkylation with Orthoesters and a New Participation of the Cyano Group in the Rearrangement
  18. Synthesis and Thermal Properties of Twin Compounds, Alkanediacids 4-(4'-Cyano)-biphenyl Diesters
  19. Synthesis of Pyrrolo-, Thienopyrrolo-, Benzothienopyrroloquinolines as well as Triazoloindole Derivatives
  20. Ab initio MO Optimizations of Osmiumtetracarbonyldihydride and Metallacyclophanes with two Osmium Atoms and their Molecular Complexes with Different Guests
  21. Preparation and Crystal Structure of Cs4Nb2S11
  22. On the Metalation of 2,6-Dimethyl-4-tert-butyl-thiophenol
  23. Kristallstruktur des Oxo-Acetatkomplexes [Co7(μ4- O)2(O2CCH3)10(OPEt3)2] / Crystal Structure of the Oxo-Acetate Complex [Co7(μ4 -O)2(O2CCH3)10(OPEt3)2]
  24. Penol Catalyzed Claisen ortho Ester Rearrangment of Allylic Alcohols with Trimethyl-β-hoxy) ortho Propionate
https://doi.org/10.1515/znb-1998-1005
Keywords for this article
Silylamines; Alkylamines; Borane Adducts; Amineboranes; Basicity Studies

Articles in the same Issue

  1. Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LIX [1], Ein Addukt des Me3P-substituierten Ferrio-diphenylphosphans Cp(OC)(Me3P)Fe-PPh2 mit Methylisothiocyanat: Darstellung, Protonierung und Methylierung / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LIX [1]. An Adduct of the Me3P-Substituted Ferrio-diphenylphosphane Cp(OC)(Me3P)Fe-PPh2 and Methylisothiocyanate: Synthesis, Protonation, and Methylation
  2. Ubergangsmetall-substituierte Phosphane, Arsane und Stibane, LX [1]. Ferrio-(thiocarbamoyl)phosphane Cp(OC)2 Fe-P(Mes)[C(=S)-N(R)H] (R = Me, Et, f-Bu): Aufbau aus dem Ferrio-mesitylphosphan Cp(OC)2 Fe-P(Mes)H und Organoisothiocyanaten sowie Quaternisierung mit Alkylhalogeniden und Oxidation mit Schwefel / Transition Metal Substituted Phosphanes, Arsanes and Stibanes, LX [1]. Ferrio-(thiocarbamoyl)phosphanes Cp(OC)2Fe-P(Mes)[C(=S)-N(R)H] (R= Me, Et, r-Bu): Build-up from the Ferrio-mesitylphosphane Cp(OC)2Fe-P(Mes)H and Organoisothiocyanates, Quatemization with Alkyl Halides and Oxidation with Sulfur
  3. Phosphenium-Komplexe, 43 [1]. Ringöffnungsreaktionen der dreigliedrigen Phosphametallacyclen {PR2 = P(o-Tol)2, P(Ph)(o-Tol), P(Mes)[C(S)N(H)Et], P(/-Bu)[C(O)N(H)Et} / Phosphenium Complexes, 43 [1]. Ring-Opening Reactions of the Three-Membered Phosphametallacycles {PR1 = P(o-Tol)2, P(Ph)(oTol), P(Mes)[C(S)N(H)Et], P(r-Bu)[C(0)N(H)Et}
  4. Magnesium Bis[D(-)-Mandelate] Dihydrate and Other Alkaline Earth, Alkali, and Zinc Salts of Mandelic Acid
  5. The Basicity of Silylamines and Alkylamines: An Equilibrium Study of the Competitive Borane Adduct Formation
  6. Kristallchemische Beziehungen von CO6O2 [TeO4 (CoAsO5)2] zur Steinsalzstruktur von CoO mit einem Beitrag über magnetische Messungen an CO6O2[TeO4(CoAsO5)2] / Crystal Chemical Relations of Co6O2[TeO4(CoAsO5)2] to the Rocksalt Structure of CoO and a Contribution on Magnetic Measurements of Co6O2[TeO4(CoAsO5)2]
  7. Synthese, Kristallstruktur und Eigenschaften von Triguanidinium-tri--imidocyclotriphosphat-Monohydrat und Tetraguanidinium-tetra-/i-imidocyclotetraphosphat-Tetrahydrat, [C(NH2)3]3(PO2NH)3 · H2O und [C(NH2)3]4(PO2NH)4 · 4 H2O / Synthesis, Crystal Structure, and Properties of Triguanidinium Tri-/i-imidocyclotriphosphate Monohydrate and Tetraguanidinium Tetra-/i-imidocyclotetraphosphate Tetrahydrate, [C(NH2)3]3(PO2NH)3 · H2O and [C(NH2)3]4(PO*NH)4 · 4 H2O
  8. Untersuchungen an Polyhalogeniden, XXXVII [1]. Heptaiodide(3-) von Amminkomplexen des Chroms und Cobalts: Hexamminchrom(III)heptaiodid [Cr(NH3)6](I3)(I4) und die Tri-μ-hydroxo-bis[metall(III)-triammin]heptaiodide [(NH3)3 M(OH)3M(NH3)3](I3)2I mit M = Co, Cr / Studies o f Polyhalides, XXXVII [1]. Heptaiodides(3-) of Ammine Complexes of Chromium and Cobalt: Hexamminechromium(III) heptaiodide [Cr(NH3)6](I3)(I4) and the Tri-μ-hydroxo-bis[metal(III)-triammine] heptaiodides [(NH3)3M(OH)3M(NH3)3](I3)2I with M = Co, Cr
  9. Functionalized 1,1-Ethene Dithiolates as Ligands, V [1]. Synthesis and Crystal Structure of Palladium(II) and Platinum(II) Complexes with Dithioylidene Barbituric Acid Ligands. Molecular Structure of a 2,6-Diaminopyridine-Platinum(II) Barbiturate Complex
  10. Solvothermal Synthesis and Crystal Structure Determination of Tris- (ethyleneamine-ammonium) Tetraselenoantimonat: Non-Centrosymmetry Mediated by an Extended Unusual N-H···N Hydrogen Bonded Network?
  11. Thermische Zersetzung und Lösungskalorimetrie von Ammoniumeuropiumchloriden / Thermal Decomposition and Solution Calorimetry of Ammonium Europium Chlorides
  12. Photochemical Reductive Elimination of Nitrogen from Triazidogallium(III). Generation of Luminescent Gallium(I)
  13. Zur Existenz von [ReNCl4-nFn]- (n = 1-3) Nitridorhenat(VI)-Gemischt- ligandkomplexen -Eine EPR-Untersuchung / EPR Evidence of [ReNCl4-n FnJ– (n = 1-3) Nitridorhenate(VI) Mixed-Ligand Complexes
  14. Synthesis and Crystal Structure of N-[(15,4R)-2-Oxo-pinanyl]-β-alanine Methylester
  15. Synthesis and Conformation of Nucleoside 5'-S-Thiosulfates
  16. Niedere Hydrate aliphatischer primärer Amine. Neue Untersuchungen zu Bildung und Struktur [1] / Lower Hydrates of Aliphatic Primary Amines. New Studies of Formation and Structure [1]
  17. Synthesis and Dimroth Rearrangement of 6-Cyano-l,2,4-triazolo- [4,3-a]pyrimidin-5- and 7-ones. A Novel Alkylation with Orthoesters and a New Participation of the Cyano Group in the Rearrangement
  18. Synthesis and Thermal Properties of Twin Compounds, Alkanediacids 4-(4'-Cyano)-biphenyl Diesters
  19. Synthesis of Pyrrolo-, Thienopyrrolo-, Benzothienopyrroloquinolines as well as Triazoloindole Derivatives
  20. Ab initio MO Optimizations of Osmiumtetracarbonyldihydride and Metallacyclophanes with two Osmium Atoms and their Molecular Complexes with Different Guests
  21. Preparation and Crystal Structure of Cs4Nb2S11
  22. On the Metalation of 2,6-Dimethyl-4-tert-butyl-thiophenol
  23. Kristallstruktur des Oxo-Acetatkomplexes [Co7(μ4- O)2(O2CCH3)10(OPEt3)2] / Crystal Structure of the Oxo-Acetate Complex [Co7(μ4 -O)2(O2CCH3)10(OPEt3)2]
  24. Penol Catalyzed Claisen ortho Ester Rearrangment of Allylic Alcohols with Trimethyl-β-hoxy) ortho Propionate
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