Azide‐Analogous Organophosphorus Chemistry: RNP₂ as a Ligand and P₂ Source

Abstract

A P2‐transfer agent: The niobium complex 1 contains the ligand η2‐PPNMes*, which can be considered as a diphosphorus‐substituted organic azide (Mes*=2,4,6‐tBu3C6H2, Np=CH2C(CH3)3, Ar=3,5‐Me2C6H3). The P2 unit released upon thermolysis of 1 is cleanly transferred to 1,3‐cyclohexadiene, giving the tetracycle 2.

Convenient Preparation and Detailed Analysis of a Series of NHC-Stabilized Phosphorus(I) Dyes and Their Derivatives

“…The compounds they investigated included some of the first examples of stable compounds that contained dicoordinate phosphorus atoms, and the structure of one of these, [ A ]­[ClO 4 ], reported by Allmann, provided evidence for 3p­(P)–2p­(C) π-bonding (Figure ). − Since that time, the chemistry of low-coordinate phosphorus compounds has remained one of the most actively studied areas in main-group chemistry, comprising investigations ranging from the very fundamental to the highly applied. − Somewhat remarkably, only a handful of phosphamethine cyanine species have ever been characterized by X-ray crystallography in the more than five decades since their initial discovery. ,, …”

Structure, Bonding, and Reactivity of Binuclear Complexes Having Asymmetric Trigonal Phosphinidene Bridges: Addition of 16-Electron Metal Carbonyl Fragments to the Dimolybdenum Compounds [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(CO)2L] and [Mo2Cp2(μ-PH)(CO)2L] (L = η6-1,3,5-C6H3tBu3)

“…The chemistry of complexes containing multiple bonds between metals and main-group elements is a fascinating field in contemporary chemistry, and these species are excellent starting materials for the synthesis of unusual ligands that are stabilized by the protective coordination sphere of the metal complex . In this context, the chemistry of transition-metal complexes having phosphinidene ligands (PR, with R = alkyl, aryl, etc.)…”

Ethylenebis(triphenylphosphine)platinum as a Probe for Niobium-Mediated Diphosphorus Chemistry

“…Perhaps it is not better illustrated than by comparing the chemistry of the abundant and notoriously stable dinitrogen molecule with the rare and reactive diphosphorus (P 2 ) molecule, a species that exists, for the most part, at extreme temperatures (above 1000 K) and low pressures. , We have recently reported on a transition-metal platform for the generation of P 2 , or its synthetic equivalent, under mild conditions . That work demonstrates the use of a niobium terminal phosphide anion for the assembly of a complexed diphosphaazide ligand, PPNMes* (Mes* = 2,4,6-tri- tert -butylphenyl), adding to a small group of heavy azide analogues. − Thermolysis of the diphosphaazide complex 1 produces the niobium(V) imido (Mes*N)Nb(N[Np]Ar) 3 ( 2 ; Np = neopentyl, Ar = 3,5-dimethylphenyl), with loss of P 2 (Scheme ). When this reaction is carried out in neat 1,3-cyclohexadiene, the formation of the formal double Diels−Alder adduct of P 2 with two diene equivalents is observed.…”