N + 2]‐Cycloadditionsreaktionen des (Arylimino)phosphenium‐Ions, [P≡NAr]+–kationische PN‐Heterocyclen mit ungewöhnlicher Struktur und Bindungssituation

Abstract

[n + 2] Cycloaddition Reactions of the (Arylimino)phosphenium Ion, [P≡NAr]+–Kationic PN Heterocycles with Unusual Structure and Bonding SituationThe iminophosphenium ion [P≡NAr]+ (Ar=2,4,6‐tBu3C6H2) (1) reacts with aminoiminophosphanes R2N–P=NtBu (R=iPr, Me3Si) (2) and alkyl azides RN3 (R=tBu, Et3C) (6) to yield the corresponding [n + 2] cycloadducts [R2NP (NAr)P(NtBu)+ (3) and [PN(Ar)NNN(R)]+ (7), respectively. Single‐crystal X‐ray diffraction studies show that 3a can be considered as an intramolecular donor‐acceptor complex while 7 can be regarded as a cyclic diaminophosphenium cation coupled to a diimine fragment, which is in accordance with results of ab initio calculations.