The Reaction of White Phosphorus with NO+/NO2+[Al(ORF)4]−: The [P4NO]+ Cluster Formed by an Unexpected Nitrosonium Insertion

Köchner, Tobias; Riedel, Sebastian; Lehner, Anna J.; Scherer, Harald; Raabe, Ines; Engesser, Tobias A.; Scholz, Franziska; Gellrich, Urs; Eiden, Philipp; Schmidt, Roberto A. Paz; Plattner, Dietmar A.; Krossing, Ingo

doi:10.1002/anie.201003031

Cited by 47 publications

(27 citation statements)

References 79 publications

(39 reference statements)

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“…However,t here are myriads of further applications that are much easier to realize using the advice given in this Review.Goa head and try! Angewandte Chemie Reviews [6,133] ;K [462] ;C s [7] ;Tl [463] Cu(NCMe) 6 [464] ; Cu(NCPh) 6 [464] ; Zn(NCMe) 6 [465] Ag [133] ;Ag(CH 2 Cl 2 ) [6] ;Ag(1,2- [6] ;A g(C 6 H 4 (CF 3 ) 2 ) [6] ;A g-(NCMe) 4 [462] ;Cu(CO) 4 [459] ;Cu(CO)-(CH 2 Cl 2 ) 3 [459] ;C u(1,2-C 6 H 4 F 2 ) 2 [338] ;C u-(NCMe) 4 [466] ;Au(NCMe) 2 [40] NO [135] ; NO 2 [295] ; NS 2 [467] [Ph 3 C] [7] Et 2 O [133,134] ; THF [134] ; C 6 H 3 Me 3 [130] Me [437] ;E t [437] ; Bu [437] [Al(OC(Me)(CF 3 ) 2 ) 4 ] À Li [6,133] ;Tl [120] Ag [133] ;Ag(CH 2 Cl 2 ) [6] ;Ag(CO) [459] ;C u-(CO) 2 [459] ;Cu(CH 2 Cl 2 ) [338] Me [437] ;E t [437] ; Bu [437] [Al(OR HF ) 4 ] À Li [6,133] ;Cs [7] ;T l [120] Ag…”

Section: Resultsmentioning

confidence: 99%

“…[292,293] Although weaker oxidants than [O 2 ] + ,t he [NO] + and [NO 2 ] + salts of WCAsa re readily accessible through salt metathesis reactions in liquid SO 2 ,and the available precursors for these oxidants are detailed in Table 10. [135,294,295] 4 ]w ith an excess of white phosphorus yields the true oxidation product, the first homopolyatomic phosphorus cation [P 9 ] + . [296] Triarylammoniumyl [N(Aryl) 3 ]C + Radicals as Oxidants: Tr iarylammoniumyl cations are an interesting class of oxidants,a st he strength of the oxidant can be tuned through substituents on the aryl rings and the oxidation potential can vary from 0.16 to 1.72 Vv ersus Fc/Fc + upon changing from [N(4-MeOC 6 H 4 ) 3 ]C + to [N(C 6 Cl 5 ) 3 ]C + .…”

Section: Direct Oxidationmentioning

confidence: 99%

“…[292,293] Although weaker oxidants than [O 2 ] + ,t he [NO] + and [NO 2 ] + salts of WCAsa re readily accessible through salt metathesis reactions in liquid SO 2 ,and the available precursors for these oxidants are detailed in Table 10. [135,294,295] Thes trength and utility of both the [NO] + and [NO 2 ] + salts of [Al(OR F ) 4 ] À as an oxidant is elegantly demonstrated by the oxidation of white phosphorus to yield [P 4 NO][Al(OR F ) 4 ], with both oxidants forming the same cationic species by the unprecedented formal insertion of [NO] + into aP ÀPb ond. [295] Furthermore,t he reaction of [NO][Al(OR F ) 4 ]w ith an excess of white phosphorus yields the true oxidation product, the first homopolyatomic phosphorus cation [P 9 ] + .…”

Section: Direct Oxidationmentioning

confidence: 99%

“…[135,294,295] Thes trength and utility of both the [NO] + and [NO 2 ] + salts of [Al(OR F ) 4 ] À as an oxidant is elegantly demonstrated by the oxidation of white phosphorus to yield [P 4 NO][Al(OR F ) 4 ], with both oxidants forming the same cationic species by the unprecedented formal insertion of [NO] + into aP ÀPb ond. [295] Furthermore,t he reaction of [NO][Al(OR F ) 4 ]w ith an excess of white phosphorus yields the true oxidation product, the first homopolyatomic phosphorus cation [P 9 ] + . [296] Triarylammoniumyl [N(Aryl) 3 ]C + Radicals as Oxidants: Tr iarylammoniumyl cations are an interesting class of oxidants,a st he strength of the oxidant can be tuned through substituents on the aryl rings and the oxidation potential can vary from 0.16 to 1.72 Vv ersus Fc/Fc + upon changing from [N(4-MeOC 6 H 4 ) 3 ]C + to [N(C 6 Cl 5 ) 3 ]C + .…”

Section: Direct Oxidationmentioning

confidence: 99%

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Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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This Review gives a comprehensive overview of the most topical weakly coordinating anions (WCAs) and contains information on WCA design, stability, and applications. As an update to the 2004 review, developments in common classes of WCA are included. Methods for the incorporation of WCAs into a given system are discussed and advice given on how to best choose a method for the introduction of a particular WCA. A series of starting materials for a large number of WCA precursors and references are tabulated as a useful resource when looking for procedures to prepare WCAs. Furthermore, a collection of scales that allow the performance of a WCA, or its underlying Lewis acid, to be judged is collated with some advice on how to use them. The examples chosen to illustrate WCA developments are taken from a broad selection of topics where WCAs play a role. In addition a section focusing on transition metal and catalysis applications as well as supporting electrolytes is also included.

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Section: Resultsmentioning

confidence: 99%

Section: Direct Oxidationmentioning

confidence: 99%

“…[292,293] Although weaker oxidants than [O 2 ] + ,t he [NO] + and [NO 2 ] + salts of WCAsa re readily accessible through salt metathesis reactions in liquid SO 2 ,and the available precursors for these oxidants are detailed in Table 10. [135,294,295] Thes trength and utility of both the [NO] + and [NO 2 ] + salts of [Al(OR F ) 4 ] À as an oxidant is elegantly demonstrated by the oxidation of white phosphorus to yield [P 4 NO][Al(OR F ) 4 ], with both oxidants forming the same cationic species by the unprecedented formal insertion of [NO] + into aP ÀPb ond. [295] Furthermore,t he reaction of [NO][Al(OR F ) 4 ]w ith an excess of white phosphorus yields the true oxidation product, the first homopolyatomic phosphorus cation [P 9 ] + .…”

Section: Direct Oxidationmentioning

confidence: 99%

Section: Direct Oxidationmentioning

confidence: 99%

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Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

et al. 2018

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“…Nitrosyl salts of WCAs represent very useful oxidants in synthetic chemistry,f or example, for reactive cations, [29] maingroup dications, [30] monocations, [31] and adducts like [P 4 NO] + [32] or [R 2 S 2 NO] + . [32,33] 4 ] À (1d)i np articulara lready provedi ts suitability as astarting materialfor main-group chemistry.…”

Section: Synthesis Of Nitrosyl Salts Of Weakly Coordinating Anionsmentioning

confidence: 99%

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Engesser

Friedmann

Martens

et al. 2016

Chemistry A European J

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A series of gold acetonitrile complexes [Au(NCMe) ] [WCA] with weakly coordinating counterions (WCAs) was synthesized by the reaction of elemental gold and nitrosyl salts [NO] [WCA] in acetonitrile ([WCA] =[GaCl ] , [B(CF ) ] , [Al(OR ) ] ; R =C(CF ) ). In the crystal structures, the [Au(NCMe) ] units appeared as monomers, dimers, or chains. A clear correlation between the aurophilicity and the coordinating ability of counterions was observed, with more strongly coordinating WCAs leading to stronger aurophilic contacts (distances, C-N stretching frequencies of [Au(NCMe) ] units). An attempt to prepare [Au(L) ] units, even with less weakly basic solvents like CH Cl , led to decomposition of the [Al(OR ) ] anion and formation of [NO(CH Cl ) ] [F(Al(OR ) ) ] . All nitrosyl reagents [NO] [WCA] were generated according to an optimized procedure and were thoroughly characterized by Raman and NMR spectroscopy. Moreover, the to date unknown species [NO] [B(CF ) CN] was prepared. Its reaction with gold unexpectedly produced [Au(NCMe) ] [Au(NCB(CF ) ) ] , in which the cyanoborate counterion acts as an anionic ligand itself. Interestingly, the auroborate anion [Au(NCB(CF ) ) ] behaves as a weakly coordinating counterion, which becomes evident from the crystallographic data and the vibrational spectral characteristics of the [Au(NCMe) ] cation in this complex. Ligand exchange in the only room temperature stable salt of this series, [Au(NCMe) ] [Al(OR ) ] , is facile and, for example, [Au(PPh )(NCMe)] [Al(OR ) ] can be selectively generated. This reactivity opens the possibility to generate various [AuL L ] [Al(OR ) ] salts through consecutive ligand-exchange reactions that offer access to a huge variety of Au complexes for gold catalysis.

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Endlich positiv: [P₉]⁺[Al{OC(CF₃)₃}₄]⁻, das Salz eines homopolyatomaren Phosphorkations

et al. 2012

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Professor Dieter Naumann zum 70. Geburtstag gewidmet Seit seiner ersten Entdeckung durch Hennig Brand im Jahr 1669 fasziniert elementarer Phosphor Wissenschaftler auf der ganzen Welt. [1][2][3][4] Der metastabile weiße Phosphor wird derzeit jährlich im Millionen-Tonnen-Maßstab produziert, und Phosphorverbindungen finden weitreichende Anwendungen in der Chemie, der Materialforschung und den Biowissenschaften. Zurzeit sind sechs Modifikationen des elementaren Phosphors bekannt, von denen drei erst 2004 und 2005 entdeckt wurden. [5,6] Reine Phosphoranionen [P n ] xÀ sind seit 1955 [7] in hunderten Verbindungen und mit fast jeder Kombination an n und x bekannt. [8] Sie haben teilweise sehr interessante und zu Beginn unerwartete Eigenschaften, z. B. die reversible Interkalation von Lithiumionen, wodurch sie sich als Elektrodenmaterial für Lithiumionenbatterien eignen. [9] Elementarer und auch anionischer Phosphor tendieren zur P-P-Bindungsbildung, was zur Verknüpfung der Atome in molekularen sowie ein-, zwei-und dreidimensionalen Festkçrperstrukturen führt. Ungeachtet der Strukturvielfalt der neutralen und anionischen (Poly)phosphorverbindungen und der relativ starken P-P-Einfachbindung (ca. 200 kJ mol À1 ) sind gegenwärtig keine reinen (Poly)phosphorkationen in der kondensierten Phase bekannt. Einige Beispiele für kationische Phosphorcluster wie [P 5 X 2 ] + (X = Cl, [10] Br, I [11] ), die Serie [P 5 Ph 2 ] + , [P 6 Ph 4 ] + und [P 7 Ph 6 ] +[12] oder auch das kürzlich beschriebene [P 4 R 2 ] 2+ (R =-PPh 3 , -AsPh 3 ) [13] kçnnen in der Literatur gefunden werden. Massenspektrometrische Untersuchungen [14] und quantenchemische Rechnungen [15,16] in der Gasphase ergaben, dass die diamagnetischen Clusterkationen [P n ] + mit ungeradem n stabiler als die paramagnetischen mit

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The Reaction of White Phosphorus with NO⁺/NO₂⁺[Al(OR^F)₄]⁻: The [P₄NO]⁺ Cluster Formed by an Unexpected Nitrosonium Insertion

Cited by 47 publications

References 79 publications

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Endlich positiv: [P₉]⁺[Al{OC(CF₃)₃}₄]⁻, das Salz eines homopolyatomaren Phosphorkations

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The Reaction of White Phosphorus with NO+/NO2+[Al(ORF)4]−: The [P4NO]+ Cluster Formed by an Unexpected Nitrosonium Insertion

Cited by 47 publications

References 79 publications

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions

Homoleptic Gold Acetonitrile Complexes with Medium to Very Weakly Coordinating Counterions: Effect on Aurophilicity?

Endlich positiv: [P9]+[Al{OC(CF3)3}4]−, das Salz eines homopolyatomaren Phosphorkations

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The Reaction of White Phosphorus with NO⁺/NO₂⁺[Al(OR^F)₄]⁻: The [P₄NO]⁺ Cluster Formed by an Unexpected Nitrosonium Insertion

Endlich positiv: [P₉]⁺[Al{OC(CF₃)₃}₄]⁻, das Salz eines homopolyatomaren Phosphorkations