𝔖 Bobbio Scriptorium
✦   LIBER   ✦

On the Ring-Expansion in Aromatic Nitrenes and Carbenes

✍ Scribed by Rolf Gleiter; Wolfgang Rettig; Curt Wentrup

Book ID
102858342
Publisher
John Wiley and Sons
Year
1974
Tongue
German
Weight
698 KB
Volume
57
Category
Article
ISSN
0018-019X

No coin nor oath required. For personal study only.

✦ Synopsis

Abstract

The ring expansion, phenylnitrene (1) → azepinylidene (3) has been investigated using the CNDO/2 and Extended Hückel method. Both methods predict that the nitrene‐nitrogen of 1 is moving out of the molecular plane on the path of minimum energy. Whether an intermediate 2 is formed or not, the net charge during the reaction indicates that an interaction between the filled nitrene p‐orbital and an empty MO of the ring is important in lowering the transition state. The results are compared with experimental results of arylnitrenes and arylcarbenes. The rearrangement of tolylcarbenes to benzocyclobutene and styrene has been reexamined experimentally and interpreted in terms of the dynamics of the out of plane movement of the carbene during ring expansion.

📜 SIMILAR VOLUMES

The Ring Expansion – Ring Contraction Di
The Ring Expansion – Ring Contraction Dichotomy in Aromatic Nitrene and Carbene Reactions I. Arylcarbenes. Preliminary communication
✍ C. Wentrup; C. Mayor; R. Gleiter 📂 Article 📅 1972 🏛 John Wiley and Sons 🌐 German ⚖ 306 KB

## Abstract Rearrangement experiments and energy calculations by the CNDO/2 and extende __Hückel__ methods indicate that ring expansion and ring contraction in aromatic carbenes and nitrnes __can__ be one‐step processes which are governed by the stabilities of the primary products and the energies

The Ring Expansion - Ring Contraction Di
The Ring Expansion - Ring Contraction Dichotomy in Aromatic Nitrene and Carbene Reactions II. Hetarylnitrenes. Preliminary communication
✍ C. Wentrup; C. Thétaz; R. Gleiter 📂 Article 📅 1972 🏛 John Wiley and Sons 🌐 German ⚖ 260 KB

## Abstract ^15^N‐labelling experiments and energy calculations on nitreno‐azines and ‐diazies are in agreement and lead to the theory that both ring contraction and ring expansion in hetarylnitrenes __can__ be one‐step processes which are governed mainly by the energy differences between the react

Picosecond laser studies on the effect o
Picosecond laser studies on the effect of structure and environment on intersystem crossing in aromatic carbenes
✍ J.G. Langan; E.V. Sitzmann; K.B. Eisenthal 📂 Article 📅 1984 🏛 Elsevier Science 🌐 English ⚖ 591 KB

A large solvent polarity effect on the rate of singlet to triplet intersystem crossing (ksT) has been observed in the carbenes, diphenylcarbene (DPC) and dicycloheptadienylidene (DCHD)-it is found that both ksT and the energy splitting (A&T) separtaing the singlet and triplet states decrease as the