On New Staudinger Type Reactions of Phosphorus Centered Biradicaloids, [P(μ-NR)]2 (R = Ter, Hyp), with Ionic and Covalent Azides

被引：2

作者：

Schulz, Axel ^{[1
,2
]}

Hinz, Alexander ^{[1
]}

Rolke, Anne ^{[1
]}

Villinger, Alexander ^{[1
]}

Wustrack, Ronald ^{[1
]}

机构：

[1] Univ Rostock, Anorgan Chem, Inst Chem, Albert Einstein Str 3a, D-18059 Rostock, Germany

[2] Univ Rostock, Leibniz Inst Katalyse, Albert Einstein Str 29a, D-18059 Rostock, Germany

来源：

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 2021年 / 647卷 / 04期

关键词：

Azide; Phosphorus; Staudinger reaction; Biradicaloid; Reaction mechanisms; MAIN-GROUP ELEMENTS; FRUSTRATED LEWIS PAIRS; MOLECULAR-STRUCTURE; NON-KEKULE; ACTIVATION; CARBENES; REACTIVITY; RADICALS; HYDROGEN; BEHAVIOR;

D O I：

10.1002/zaac.202000228

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Phosphorus centered biradicaloids of the type [P(mu-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 (AgN3 and Hg(N-3)(2)). While the reaction with the ionic azides led exclusively to the formation of diazides, [N3P(mu-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.

引用

页码：245 / 257

页数：13