Functionalization of P<sub>4</sub> in the coordination sphere of coinage metal cations

Borger, Jaap E.; Bakker, Martijn S.; Ehlers, Andreas W.; Lutz, Martin; Slootweg, J. Chris; Lammertsma, Koop

doi:10.1039/c5cc10037b

Cited by 27 publications

(16 citation statements)

References 41 publications

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“…Lammertsma and co‐workers recently reported that the N ‐heterocyclic carbene (NHC) gold complex 90 readily reacts with aryl lithium compounds at low temperatures (Scheme 15 c). [52] The controlled P−C bond formation and concomitant cleavage of one P−P bond gives rise to the proposed intermediate butterfly species 91 . Immediate addition of a second [(NHC)Au] fragment, derived through formal loss of P 4 from a second equivalent of 90 , affords the cationic complex 92 in high yield.…”

Section: Transition‐metal‐mediated Functionalization Of White Phosphorusmentioning

confidence: 99%

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Hoidn

Scott

Wolf

2020

Chemistry A European J

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Recently there has been great interest in the reactivity of transition‐metal (TM) centers towards white phosphorus (P4). This has ultimately been motivated by a desire to find TM‐mediated alternatives to the current industrial routes used to transform P4 into myriad useful P‐containing products, which are typically indirect, wasteful, and highly hazardous. Such a TM‐mediated process can be divided into two steps: activation of P4 to generate a polyphosphorus complex TM‐Pn, and subsequent functionalization of this complex to release the desired phosphorus‐containing product. The former step has by now become well established, allowing the isolation of many different TM‐Pn products. In contrast, productive functionalization of these complexes has proven extremely challenging and has been achieved only in a relative handful of cases. In this review we provide a comprehensive summary of successful TM‐Pn functionalization reactions, where TM‐Pn must be accessible by reaction of a TM precursor with P4. We hope that this will provide a useful resource for continuing efforts that are working towards this highly challenging goal of modern synthetic chemistry.

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Section: Transition‐metal‐mediated Functionalization Of White Phosphorusmentioning

confidence: 99%

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Hoidn

Scott

Wolf

2020

Chemistry A European J

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“…The isolation and versatility of the stabilized [RP 4 ] − anion 4 marks a significant step toward the controlled functionalization of P 4 with organolithium reagents. Interestingly, related RP 4 derivatives can also be generated from P 4 in the coordination sphere of a gold(I) cation, even with unencumbered MesLi, which is otherwise precluded due to rapid quenching with boron Lewis acids to Li[MesBAr 3 ]. Exemplary is the reaction of ArylLi with the η 2 ‐P 4 ‐coordinated cationic (NHC)Au I complex 12 (Scheme ; Aryl=Mes or Dmp, NHC= N ‐heterocyclic carbene) that afforded selectively the neutral bicyclic tetraphosphanes 13 , which coordinates to an additional gold cation complex with displacement of a P 4 molecule to give bimetallic 14 .…”

Section: Functionalization Of P4 Using Main Group Metal Organylsmentioning

confidence: 99%

Functionalization of P₄ through Direct P−C Bond Formation

Borger

Ehlers

Slootweg

et al. 2017

Chemistry A European J

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Research on chlorine‐free conversions of P4 into organophosphorus compounds (OPCs) has a long track record, but methods that allow desirable, direct P−C bond formations have only recently emerged. These include the use of metal organyls, carbenes, carboradicals, and photochemical approaches. The versatile product scope enables the preparation of both industrially relevant organophosphorus compounds, as well as a broad range of intriguing new compound classes. Herein we provide a concise overview of recent breakthroughs and outline the acquired fundamental insights to aid future developments.

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“…On the contrary, concerning P 4 and polyphosphorus (P n ) complexes, fewer Au coordination compounds are known. Reactions of Au(I)Cl species with a chloride abstractor (e.g., GaCl 3 or LiTEF) and P 4 led to discrete coordination compounds . Interestingly, Forfar et al carried out similar reactions with Cu and Ag salts as well .…”

Section: Introductionmentioning

confidence: 99%

Au-Containing Coordination Polymers Based on Polyphosphorus Ligand Complexes

et al. 2021

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Whereas the self-assembly of pentaphosphaferrocenes [Cp R Fe(η 5 -P 5 )] (Cp R = Cp*, Cp × , and Cp Bn ) with Cu and Ag salts has been well-studied in the past, the coordination chemistry toward Au complexes has been left untouched so far. Herein, the results of the self-assembly processes of [Cp R Fe(η 5 -P 5 )] with Au salts of different anions (GaCl 4 − , SbF 6 − , and Al(OC(CF 3 ) 3 ) 4 (TEF − )) are reported. Next to a variety of molecular coordination products, the first coordination polymers based on polyphosphorus ligand complexes and Au salts are also obtained. Thereby, a 2D coordination polymer comprising metal vacancies is isolated. In all products, the Au centers are coordinated in a linear or a trigonal planar environment. In solution, highly dynamic processes are observed. Variable-temperature NMR spectroscopy, solid-state NMR spectroscopy, and X-ray powder diffraction were applied to gain further insight into selected coordination compounds.

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Functionalization of P₄ in the coordination sphere of coinage metal cations

Abstract: Selective functionalization of white phosphorus is achieved by addition of ArLi to unique cationic coinage metal η2–P4 complexes.

Cited by 27 publications

References 41 publications

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Functionalization of P₄ through Direct P−C Bond Formation

Au-Containing Coordination Polymers Based on Polyphosphorus Ligand Complexes

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Functionalization of P4 in the coordination sphere of coinage metal cations

Abstract: Selective functionalization of white phosphorus is achieved by addition of ArLi to unique cationic coinage metal η2–P4 complexes.

Cited by 27 publications

References 41 publications

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Transition‐Metal‐Mediated Functionalization of White Phosphorus

Functionalization of P4 through Direct P−C Bond Formation

Au-Containing Coordination Polymers Based on Polyphosphorus Ligand Complexes

Contact Info

Product

Resources

About

Functionalization of P₄ in the coordination sphere of coinage metal cations

Functionalization of P₄ through Direct P−C Bond Formation