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- Title
Synthesis, Structure, and Reactivity of Diazene Adducts: Isolation of iso-Diazene Stabilized as a Borane Adduct.
- Authors
Reiß, Fabian; Schulz , Axel; Villinger, Alexander
- Abstract
This work describes the synthesis and full characterization of a series of GaCl3 and B(C6F5)3 adducts of diazenes R1NNR2 (R1=R2=Me3Si, Ph; R1=Me3Si, R2=Ph). Trans-PhNNPh forms a stable adduct with GaCl3, whereas no adduct, but instead a frustrated Lewis acid-base pair is formed with B(C6F5)3. The cis-PhNNPh ⋅B(C6F5)3 adduct could only be isolated when UV light was used, which triggers the isomerization from trans- to cis-PhNNPh, which provides more space for the bulky borane. Treatment of trans-PhNNSiMe3 with GaCl3 led to the expected trans-PhNNSiMe3 ⋅GaCl3 adduct but the reaction with B(C6F5)3 triggered a 1,2-Me3Si shift, which resulted in the formation of a highly labile iso-diazene, Me3Si(Ph)NN; stabilized as a B(C6F5)3 adduct. Trans-Me3SiNNSiMe3 forms a labile cis-Me3SiNNSiMe3 ⋅B(C6F5)3 adduct, which isomerizes to give the transient iso-diazene species (Me3Si)2NN ⋅B(C6F5)3 upon heating. Both iso-diazene species insert easily into one BC bond of B(C6F5)3 to afford hydrazinoboranes. All new compounds were fully characterized by means of X-ray crystallography, vibrational spectroscopy, CHN analysis, and NMR spectroscopy. All compounds were further investigated by DFT and the bonding situation was assessed by natural bond orbital (NBO) analysis.
- Subjects
DIAZENES; CHEMICAL adducts; MOLECULAR structure of boranes; REACTIVITY (Chemistry); NATURAL orbitals
- Publication
Chemistry - A European Journal, 2014, Vol 20, Issue 37, p11800
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201402921