title: Synthesis, structure, and reactivity of diazene adducts: isolation of iso-diazene stabilized as a borane adduct.
abstract: This work describes the synthesis and full characterization of a series of GaCl3 and B(C6 F5 )3 adducts of diazenes R(1) NNR(2) (R(1) =R(2) =Me3 Si, Ph; R(1) =Me3 Si, R(2) =Ph). Trans-PhNNPh forms a stable adduct with GaCl3 , whereas no adduct, but instead a frustrated Lewis acid-base pair is formed with B(C6 F5 )3 . The cis-PhNNPh⋅B(C6 F5 )3 adduct could only be isolated when UV light was used, which triggers the isomerization from trans- to cis-PhNNPh, which provides more space for the bulky borane. Treatment of trans-PhNNSiMe3 with GaCl3 led to the expected trans-PhNNSiMe3 ⋅GaCl3 adduct but the reaction with B(C6 F5 )3 triggered a 1,2-Me3 Si shift, which resulted in the formation of a highly labile iso-diazene, Me3 Si(Ph)NN; stabilized as a B(C6 F5 )3 adduct. Trans-Me3 SiNNSiMe3 forms a labile cis-Me3 SiNNSiMe3 ⋅B(C6 F5 )3 adduct, which isomerizes to give the transient iso-diazene species (Me3 Si)2 NN⋅B(C6 F5 )3 upon heating. Both iso-diazene species insert easily into one BC bond of B(C6 F5 )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.
authors: Institut für Chemie, Abteilung Anorganische Chemie, Universität Rostock, Albert-Einstein-Strasse 3a, 18059 Rostock (Germany).
authors: Fabian
authors: F
authors: Reiß
authors: Axel
authors: A
authors: Schulz
authors: Alexander
authors: A
authors: Villinger
keywords: boron; diazenes; frustrated Lewis pairs; gallium; hydrazinoboranes