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On New Staudinger Type Reactions of Phosphorus Centered Biradicaloids, [P(μ‐NR)] 2 (R = Ter, Hyp), with Ionic and Covalent Azides
Author(s) -
Schulz Axel,
Hinz Alexander,
Rölke Anne,
Villinger Alexander,
Wustrack Ronald
Publication year - 2021
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202000228
Subject(s) - chemistry , staudinger reaction , covalent bond , ionic bonding , trimethylsilyl , azide , medicinal chemistry , tris , silylation , phosphorus , organic chemistry , ion , catalysis , biochemistry
Phosphorus centered biradicaloids of the type [P(μ‐NTer)] 2 [R = Ter = terphenyl = 2,6‐bis(2,4,6‐trimethylphenyl)phenyl, Hyp = tris(trimethylsilyl)silyl] were treated with covalent (R‐N 3 ) and ionic azides (AgN 3 and Hg(N 3 ) 2 ). While the reaction with the ionic azides led exclusively to the formation of diazides, [N 3 P(μ‐NTer)] 2 , triaza‐diphospha‐pentadienes, RN=P–N(R')–P=NR, were observed in the reaction with covalent azides featuring a Staudinger type reaction followed by PN bond rearrangement reactions. This new Staudinger type mechanism as well as the structure, bonding and thermodynamics along different reaction paths are discussed based on DFT computations.