Chemistry Reference
In-Depth Information
THEORY AND COMPUTATION IN
THE STUDY OF NITRENES AND
THEIR EXCITED-STATE
PHOTOPRECURSORS
S
HUBHAM
V
YAS
,A
RTHUR
H. W
INTER
,
AND
C
HRISTOPHER
M. H
ADAD
2.1 Introduction
2.2 Structural and Electronic Properties of Nitrenes
2.2.1 The Electronic Landscape of Nitrenes
2.2.2 Singlet Electronic States of Nitrenes
2.2.3 Ambiguity of Singlet State Nitrene Configuration Designations as “Open-Shell”
or “Closed-Shell”
2.2.4 Singlet-Triplet Gap of Nitrenes
2.2.5 Substituent Effects on Singlet Nitrene Configuration
2.2.6 Electronic Structure of Carbonylnitrenes
2.2.7 Comparison of the Molecular Structure Between Singlet and Triplet Phenylnitrene
2.2.8 Choice of Computational Method for Modeling Nitrenes
2.3 The Central Role of the Singlet Nitrene
2.3.1 Structural and Electronic Influences on the Rate of Nitrene Intersystem Crossing
2.3.2 Energy Barriers and Thermodynamics of Diazirine Formation
2.3.3 Protonation of Nitrenes to Yield Nitrenium Ions
2.3.4 Extending Singlet Nitrene Lifetime Through Inhibition of Alternative Decay
Channels
2.3.5 Possibility of Excited State Nitrene Reactions—Exceptions to Kasha's Rule?
2.4 Precursors to the Nitrene
2.4.1 Different Precursors to Nitrene Formation
2.4.2 Geometry and Electronic Structure of Azides
2.5 Structure and Photochemistry of Homo-Azides
2.5.1 Alkyl Azides
