Nitrogen-15 NMR spectrum of a 1,1-diazene. N-(2,2,6,6-tetramethylpiperidyl)nitrene

Bis(trimethylsilyl)diazene revisited. Density functional theory (DFT) calculations of nitrogen NMR parameters of some azo‐compounds

“…The effect of the cis-or trans-configuration on the magnitude of 1 J ( 15 N, 13 C) in azo-compounds has been noted [38], and is correctly reproduced by the calculations. For X = 29 Si, the situation is comparable with that for 13 14 N) is in agreement with the experimental evidence obtained here for 6a (vide supra). In the nitrenes, the lone pair of electrons at the aminonitrogen atom is engaged in bonding, and it is therefore expected that the contact contribution is less affected than in the azo-compounds.…”

“…The calcd. value 1 J (N,N) for 15 is very close to the experimental one [14], and this suggests that the calcd. negative sign is correct.…”

“…It has been shown that the calculation of nuclear magnetic shielding provides fairly accurate data or at least predicts most trends correctly [11][12][13]. In this context, the extreme nuclear magnetic deshielding of nitrogen in Me 3 Si N N SiMe 3 6a (δN = +615) [4] or in N- (2,2,6,6-tetramethylpiperidyl)nitrene 15 (δN −58.8 and +536.8) [14] are of interest, since they may serve as a test for the performance of theoretical models. More recently, progress has been made in the calculations of indirect nuclear spin-spin coupling constants by coupled perturbed DFT methods [12,[15][16][17], and these have been already applied successfully to numerous classes of compounds [18][19][20][21][22].…”

Synthesis, Structure, and Reactivity of Diazene Adducts: Isolation of iso‐Diazene Stabilized as a Borane Adduct

“…It should be mentioned that thermal treatment of adduct 4 led to dissociation of the adduct and small amounts of unidentified decomposition products (see Figure S20 in the Supporting Information). Moreover, it is interesting to note that we did not observe dimerization of the iso ‐diazene adduct species (as for N ‐(2,2,6,6‐tetramethylpiperidyl)nitrene) to yield the tetrazene R 2 NNNNR 2 7. For 2 it was also shown by Wiberg et al.…”

Benchmark ab initio thermochemistry of the isomers of diimide, N2H2, using accurate computed structures and anharmonic force fields

“…Following earlier reporting of the synthesis of the substituted isodiazene (2,2,6,6-tetramethylpiperidyl)nitrene [18], isolation and characterization by low-temperature matrix infrared spectroscopy was reported by Sylwester and…”