Von Fluorsilylamiden zu Element-Silylamiden und Iminosilanen
-
Michael Jendras
and
Mathias Noltemeyer
Ethyltrifluorosilane reacts with tert-butyllithium in a molar ratio 1:2 to give Et(CMe3)2SiF (1), which forms the aminosilane, Et(CMe3)2SiNH2 (2) in the reaction with NaNH2. The lithium salt of 2 and (Me3C)2SiF2 gives (Me3C)2SiF-NHSi(CMe3)2Et (3). 3 reacts with BuLi to give the lithium salt, (Me3C)2 SiF-NLi-Si(CMe3)2Et (4). tert-Butyl-(di-tert-butylfluoro)-silylaminoalanes (Me3C)2SiF-NCMe3-AlR2, R = Me (5), Et (6) are formed in the reaction of (Me3C)2SiF-NLi CMe3 (I) and ClAlR2. The lithium salt (Me3C)2SiF-NLi-Si(CMe3)2Me (III) reacts with BF3 under formation of the bis(silyl)aminodifluoroborane (Me3C)2SiF-N(BF2) Si(CMe3)2Me (7). In the reaction of I with F3SiPh rotamers of (Me3C)2SiF-NCMe3 SiF2Ph (8) are obtained.
Stannyl-silylamines are prepared in reactions of the lithium salts (Me3C)2SiF-NLiR, R = CMe3 (I), SiF(CMe3)2 (II); Si(CMe3)2Me (III) and the chlorostannanes ClSnMe3 (9,10,11) and Cl2SnPh2 (12), (Me3C)2SiF-NSnMe3-Si(CMe3)2R (9: R = F, 10: R = Me), (Me3C)2SiF-NSnMe3CMe3 (11), (Me3C)2SiF-NCMe3SnClPh2 (12). The NMR spectra of 9 and 10 prove the existence of rotamers.
The reaction of III with Me3SiOSO2 CF3 in n-hexane leads to the formation of the tris(silyl)amine 13, (Me3C)SiF-NSiMe3)2Si(CMe3)2Me. However, the analogous reaction of III and 4 with Me3SiOSO2CF3 in thf leads to the formation of the stable iminosilanes 14 and 15, (Me3C)2Si==N- Si(CMe3)R, R = Me (14), Et (15) crystal structures of 7 and 12 are presented.
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
Articles in the same Issue
- Bis(trimethylphosphan)-η5-cyclopentadienyl- tert- butylimidovanadium( III): Reaktionen mit Schwefel, Selen, Tellur und Iod
- Von Fluorsilylamiden zu Element-Silylamiden und Iminosilanen
- β-CaB4O7: A New Polymorph Synthesized under High-Pressure/High-Temperature Conditions
- New Dinuclear Mn(II) Phenanthroline Adipato Complex: Synthesis and Structural and Thermal Characterization of Mn2(phen)2(H2O)2(C6H8O4)2
- Crystal Structure and Magnetic Properties of a New Hetero-Dinuclear CuIIMnII Schiff Base Complex
- High-Pressure Preparation, Crystal Structure, and Properties of RE4B6O15 (RE = Dy, Ho) with an Extension of the “Fundamental Building Block”-Descriptors
- Novel Asymmetrical Dianionic Polyimido-Sulfur(IV)-Ylides
- Decarbonylation of Pentamethylcyclopentadienyl Tetracarbonylvanadium, Cp*V(CO)4, in the Presence of Oxygen. The X-Ray Crystal Structure Analyses of Cp*V(CO)4 and [Cp*V(O)(μ-O)]4
- Formation of a Doubly C,N-Bridged Six-Membered Metallacyclic Bis[(2-imidazolyl)zirconocene] Dication
- Metallkomplexe mit biologisch wichtigen Liganden, CL [1]. 1,1-Dithiolato-Komplex von Palladium(II), Platin(II) und Gold(I) aus Diphenylmethylenglycinester sowie N,N-Dimethylglycinester und Schwefelkohlenstoff
- Metallkomplexe mit biologisch wichtigen Liganden, CLI [1]. Metallorganische Komplexe mit R-3-(3-Pyridyl)alaninat
- Methoxyabietane Diterpenoid from the Root of Salvia phlomoides and Structural Correction of Another Diterpene from Cryptomeria japonica
- Access to Orthogonal Protected Phenols – Synthesis of a Silylated Quinol
- A New Prenylated Hydroquinone from the Roots of Garcinia atroviridis Griff ex T. Anders (Guttiferae)
- Simple Synthesis, Characterization and Structure of Diorganotin(IV) Complexes Containing the N-(2-Salicylidene)-N'-benzoylhydrazone Ligand
- Synthese monofluorierter cyclopropanoider Nucleosidanaloga
- Crystal Structure of a New Dimethyl Carbonate/2,4,6-Tris(trifluoromethyl)- 1,3,5-triazine 1:1 Adduct
- Synthesis and Molecular Structure of [Fe2Cl2(μ-S-tBu)2(η1-η1-μ-dppe)] (dppe = Ph2P(CH2)2PPh2)
Articles in the same Issue
- Bis(trimethylphosphan)-η5-cyclopentadienyl- tert- butylimidovanadium( III): Reaktionen mit Schwefel, Selen, Tellur und Iod
- Von Fluorsilylamiden zu Element-Silylamiden und Iminosilanen
- β-CaB4O7: A New Polymorph Synthesized under High-Pressure/High-Temperature Conditions
- New Dinuclear Mn(II) Phenanthroline Adipato Complex: Synthesis and Structural and Thermal Characterization of Mn2(phen)2(H2O)2(C6H8O4)2
- Crystal Structure and Magnetic Properties of a New Hetero-Dinuclear CuIIMnII Schiff Base Complex
- High-Pressure Preparation, Crystal Structure, and Properties of RE4B6O15 (RE = Dy, Ho) with an Extension of the “Fundamental Building Block”-Descriptors
- Novel Asymmetrical Dianionic Polyimido-Sulfur(IV)-Ylides
- Decarbonylation of Pentamethylcyclopentadienyl Tetracarbonylvanadium, Cp*V(CO)4, in the Presence of Oxygen. The X-Ray Crystal Structure Analyses of Cp*V(CO)4 and [Cp*V(O)(μ-O)]4
- Formation of a Doubly C,N-Bridged Six-Membered Metallacyclic Bis[(2-imidazolyl)zirconocene] Dication
- Metallkomplexe mit biologisch wichtigen Liganden, CL [1]. 1,1-Dithiolato-Komplex von Palladium(II), Platin(II) und Gold(I) aus Diphenylmethylenglycinester sowie N,N-Dimethylglycinester und Schwefelkohlenstoff
- Metallkomplexe mit biologisch wichtigen Liganden, CLI [1]. Metallorganische Komplexe mit R-3-(3-Pyridyl)alaninat
- Methoxyabietane Diterpenoid from the Root of Salvia phlomoides and Structural Correction of Another Diterpene from Cryptomeria japonica
- Access to Orthogonal Protected Phenols – Synthesis of a Silylated Quinol
- A New Prenylated Hydroquinone from the Roots of Garcinia atroviridis Griff ex T. Anders (Guttiferae)
- Simple Synthesis, Characterization and Structure of Diorganotin(IV) Complexes Containing the N-(2-Salicylidene)-N'-benzoylhydrazone Ligand
- Synthese monofluorierter cyclopropanoider Nucleosidanaloga
- Crystal Structure of a New Dimethyl Carbonate/2,4,6-Tris(trifluoromethyl)- 1,3,5-triazine 1:1 Adduct
- Synthesis and Molecular Structure of [Fe2Cl2(μ-S-tBu)2(η1-η1-μ-dppe)] (dppe = Ph2P(CH2)2PPh2)
