Phosphorus(I) Iodide:  A Versatile Metathesis Reagent for the Synthesis of Low Oxidation State Phosphorus Compounds

Abstract

An improved method for the synthesis of cyclic low oxidation state P cations is presented. The only byproducts of the reaction of phosphorus triiodide with chelating phosphines are readily removed, resulting in an easily accessible P(I) reagent with an anion that can be readily replaced through salt metathesis chemistry. These P(I) salts are surprisingly stable, even in O2 and moisture, and the origin of this unusual stability is elucidated using density functional theory calculations.

Synthesis of Heavy Dicyanamide Homologues from Air‐Stable Precursors

“…Single crystals of [dppeAs][BPh 4 ] and [dppeAs][BPh 4 ]⋅2 MeCN suitable for X‐ray diffraction were obtained over the course of the synthetic trials (see the Experimental Section and Supporting Information for the crystal structure of the [dppeCl][BPh 4 ] byproduct). The unsolvated salt is isomorphous with its phosphorus homologue, crystallizing in the spacegroup P 2 1 / n , whereas the diacetonitrile solvate crystallizes in P 1. The metrical parameters of the cations in both structures (Figure ) are very similar to those reported for other salts of [dppeAs] + …”

“…Chem.E ur.J. 2018, 24,14644 -14648 www.chemeurj.org solvated salt is isomorphousw ith its phosphorus homologue, [49] crystallizing in the spacegroup P2 1 /n,w hereas the diacetonitrile solvatec rystallizes in P1. The metricalp arameters of the cations in both structures ( Figure 2) are very similart o those reportedf or other salts of [dppeAs] + .…”

Homoleptic Pnictogen–Chalcogen Coordination Complexes

“…57 The results for 10Ch and 11Ch can also be contrasted with the electronic structure of the dication in 9Te, which features a highly positive tellurium center (natural charge +1.22) along with two TeN bonds whose Wiberg bond indices fall significantly short of unity (0.75). 28 Taken as a whole, the electronic structure analyses are consistent with a covalently bound description (Figure 6 B), rather than the dative bond description (Figure 6, A), for the dications 10Ch…”

Interpniktogenkationen: Neue Perspektiven in der Koordinationschemie

“…[7] Die häufig als Triphospheniumkationen bezeichneten Produkte kçnnen als Bis(phosphan)-Komplexe von P + , einem Akzeptor der Klasse 1A, betrachtet werden (Schema 10 a). [95,96] Unter den gleichen Bedingungen führen Dihalogenphosphane jedoch nicht zu Komplexen von Klasse-1A-Akzeptoren, sondern bilden symmetrische dikat-ionische Gerüste, in denen zwei vierfach koordinierte Phosphorzentren an ein dreifach koordiniertes Phosphorzentrum gebunden sind. B. dmpe, dppe) bilden die analogen cyclischen Derivate, für die eine Reihe von Verbindungen beschrieben wurde.…”