Chemistry Reference
In-Depth Information
TRIPLET ALKYL NITRENES
S
IVARAMAKRISHNAN
M
UTHUKRISHNAN
,R
ANAWEERA
A. A. U. R
ANAWEERA
,
AND
A
NNA
D. G
UDMUNDSDOTTIR
5.1 Introduction
5.2 Direct Photolysis and Thermal Activation of Azidoalkanes
5.3 Direct Photolysis and Thermolysis of Geminal Diazidoalkanes
5.4 Intermolecular Triplet-Sensitized Photolysis of Azidoalkanes
5.5 Intramolecular Triplet-Sensitized Photolysis of Azidoalkanes
5.5.1 Characterization of Triplet Alkyl Nitrenes in Solution
5.5.2 Solution Reactivity of Triplet Alkyl Nitrene
5.5.3 Hydrogen Atom Abstraction by Triplet Alkyl Nitrenes
5.5.4 Oxygen Trapping of Triplet Alkyl Nitrenes
5.5.5 Photoreactions that Compete with Intramolecular Energy Transfer in Alkyl Azides
5.6 Conclusions
Acknowledgments
References
5.1
INTRODUCTION
In the recent decades, several excellent reviews on nitrene intermediates have been
published.
1-18
These reviews demonstrate elegantly that the reactivity of nitrenes
is very different depending on their molecular structure and spin multiplicity. In
general, singlet nitrenes are short-lived, highly reactive intermediates that have been
used in applications such as surface modifications, cross-polymerizations, and
photoaffinity labeling. In comparison, triplet nitrene intermediates are less reactive
and longer-lived. Because of their stability and high-spin properties, it has been
