Synthesis and structural characterization of the first donor-stabilized phosphanetriylphosphonium cation: [Ar*PP(PPh3)]+(Ar*= 2,4,6-But 3C6H2)

Romanenko, V. D.; Rudzevich, Valentin L.; Русанов, Эдуард Б.; Chernega, Alexander N.; Senio, A.; Sotiropoulos, Jean‐Marc; Pfister‐Guillouzo, G.; Sanchez, M.

doi:10.1039/c39950001383

Cited by 41 publications

(60 citation statements)

References 17 publications

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“…Based on the electron charge distribution, the nature of this ligand can be described as a zwitterionic diphenyl(alkyl)phosphonium(+)diphosphenide(À) molecule, RPh 2 P (+) -P = P (À) (R = Ph 2 PCH 2 ), where the negative charge is placed on the m-Co,Pt-bridging P atom and the positive one on the opposite PPh 2 R phosphonium P atom. The average P = P bond length in the diphosphenide moiety is 2.182(4) which is longer than the value found for the only known phosphanetriylphosphonium cation (2.025(1) ) [13] and in agreement with the P=P bond length in diphosphenes coordinated to transition metals. [14] In the case at hand, the diphosphenide section of the zwitterion acts as a two-electron p-donor towards Co and, additionally, as a two-electron s-donor towards Pt II .…”

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confidence: 68%

Heterobimetallic Cooperation Mediates the Transformation of White Phosphorus into Zwitterionic catena‐Phosphonium(+)diphosphenide(−) Ligands

et al. 2008

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Dedicated to Professor Otto J. Scherer on the occasion of his 75th birthday White phosphorus, P 4 , the most reactive allotrope of the element, is readily available from rock phosphates and is widely used for the chemical manufacturing of a great variety of organophosphorus derivatives.[1] In a typical industrial procedure, P 4 is treated with Cl 2 at high temperature to yield phosphorus chlorides, which are subsequently treated with organic substrates to afford the organophosphorus derivatives. The growing worldwide market for phosphorus derivatives and increasingly rigorous environmental regulations, which ban dangerous precursors such as chlorine from largescale industrial processes, are stimulating the quest for methods that avoid chlorine and functionalize white phosphorus under milder conditions.[2] The most efficient approach in this regard would be an as-yet unknown metalcatalyzed functionalization of P 4 , [3] although several contributions from our group [4,5] and others [6] have shown the importance of stoichiometric activations mediated by bimetallic transition-metal complexes. Recently, Bertrand et al. have shown that metal-free activation of P 4 can also be achieved by using two equivalents of cyclic alkyl aminocarbenes to synergically activate white phosphorus. [7] Herein we report our findings that white phosphorus can be activated in a stepwise fashion by two different transitionmetal units, which initially activate the P 4 tetrahedron and then break the activated polyphosphorus unit into two zwitterionic diphenyl(alkyl)phosphonium(+)diphosphenide(À) molecules.The reaction of white phosphorus with Co(BF 4 ) 2 ·6 H 2 O and bis(diphenylphosphino)methane (dppm) in refluxing THF/butanol gives [Co(Ph 2 PCH 2 PPh 2 PPPPPh 2 PCH 2 PPh 2 )]-BF 4 (1-BF 4 ), whose synthesis [8] represents a turning point in the coordination chemistry of white phosphorus.[9] Complex 1 + contains a surprising P 6 ligand which originates from the nucleophilic attack of two PPh 2 ends from two different dppm ligands on the h 4 -tetraphosphabutadiene moiety formed by opening of the P 4 molecule. A perusal of the bonding distances-the external PÀP distances are shorter then the internal ones (2.172 vs. 2.197 )-has allowed Midollini and co-workers to formally attribute the oxidation state ÀI to Co and to describe the charge distribution of the new hexaphosphorus ligand as a P (+) À P = P À P = P À P (+) dication where two phosphonium moieties are formally located at each P 6 end. [8]

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confidence: 68%

Heterobimetallic Cooperation Mediates the Transformation of White Phosphorus into Zwitterionic catena‐Phosphonium(+)diphosphenide(−) Ligands

et al. 2008

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“…2%; d 31 P{ 1 H} = 43.9 and 52.5 ppm, 3 J P, P = 18.8 Hz), [10] which we tentatively ascribed to the bis-phos- 4 ]. [21] Themolecular structure of 2a (Scheme 1), [22,23] determined by X-ray crystal-structure analysis of suitable crystals of its tetraphenylborate analogue (obtained after anion exchange with NaBPh 4 in DCM), [10] displays an almost planar (P1-N1-N2-C1 173.4(7)8 8) trans arylazophosphonium moiety with adisordered azo group.The CÀNand NÀNbond lengths (1.437(7) and 1.245(6) ,r espectively) are comparable to those of the related arylazoimidazolium borates [ArN 2 (IMes)][BPh 4 ]( Ar = Mes, o/p-ClC 6 H 4 )r eported by Severin and co-workers (C-N:1 .411(2)/1.395(4)/1.455 (13); N-N:1 .265(2)/1.266(9)/1.24(2) ,r espectively), [11e] illustrating that in these cationic azo dyes,phosphines behave similar to carbenes. [10] Ther eaction of phenyldiazonium tetrafluoroborate with tBu 3 P( 1.1 equiv) in acetonitrile resulted in an immediate colour change from colourless to pink and afforded azophosphonium salt [PhN 2 (PtBu 3 )]-[BF 4 ] 2a (d 31 P{ 1 H} = 69.4 ppm;Scheme 1) as the sole product in 95 %yield upon isolation.…”

Section: Themetal-freeactivationandfunctionalizationofdinitrogenmentioning

confidence: 99%

Aryldiazonium Salts as Nitrogen‐Based Lewis Acids: Facile Synthesis of Tuneable Azophosphonium Salts

et al. 2018

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Inspired by the commercially available azoimidazolium dyes (e.g., Basic Red 51) that can be obtained from aryldiazonium salts and N-heterocyclic carbenes, we developed the synthesis of a unique set of arylazophosphonium salts. A range of colours were obtained by applying readily tuneable phosphine donor ligands and para-substituted aryldiazonium salts as nitrogen-based Lewis acids. With cyclic voltammetry, a general procedure was designed to establish whether the reaction between a Lewis acid and a Lewis base occurs by single-electron transfer or electron-pair transfer.

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“…Die Brückenkopfatome (P2) sind lediglich schwach positiv geladen (+ 0.12 e), während das ClAtom eine schwach negative Partialladung trägt (À0.16 e). Dementsprechend beträgt die Gesamtladung des P 4 Cl-Gerüsts + 1.21 e bzw.d es reinen P 4 -Bicyclus + 1.37 e.I mV ergleich mit der Neutralverbindung Mes*P 4 À370 ppm), [25,26,32,[37][38][39][40][41][44][45][46] aufgrund der positiven Ladung des P 4 -Gerüsts jedoch etwas weiter tieffeldverschoben ist. Das dreifach-koordinierte verbrückenden P-Atom (P m )weist eine moderate Hochfeldverschiebung (3a + : À89.5 ppm; 3b + : À123.6 ppm) innerhalb des typischen Bereichs auf,w ohingegen das vierfach-koordinierte P-Atom (P A )d eutlich tieffeldverschoben ist (3a + : +51.2 ppm; 3b + : +9.0 ppm), was bisher nicht bei Kernen in einem bicyclischen P 4 -Gerüst beobachtet wurde.A lle experimentellen Werte stimmen gut mit theoretischen Daten überein (Tabellen S8 und S9).…”

Section: Angewandte Chemieunclassified

Tieftemperatur‐Isolierung des bicyclischen Phosphinophosphoniumsalzes [Mes*₂P₄Cl][GaCl₄]

et al. 2015

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Ringsysteme aus Elementen der Gruppe 15 (Pniktogene, Pn) sind ein faszinierender Aspekt der Hauptgruppenchemie. [1][2][3] Insbesondere (pseudo-)halogensubstituiertecyclische Dipniktadiazane (B,S chema 1) haben sich als vielseitige Edukte für Folgereaktionen herausgestellt, etwa zur Synthese von (kurzlebigen) Verbindungen mit NPn-Mehrfachbindungen durch Cycloreversionsreaktionen (z. B. A), [4][5][6][7][8] grçßeren Ringsystemen durchC ycloadditionsreaktionen sowie Ringerweiterung [4,9,10] oder auch kationischen Spezies durch Abstraktion von Halogenen (C). [11][12][13][14][15] Infolgedessen interessieren wir uns momentan für die Chemie analoger Ringsysteme,d ie ausschließlich aus Phosphor aufgebaut sind (d. h. [XP(m-PR)] 2 ), um mçgliche Reaktionswege zu vergleichbaren, neuen Phosphorspezies aufzufinden. Berichte über bekannte,k ationische Phosphorringsysteme umfassen beispielsweise Phosphinophosphoniumstrukturen (I-III,S chema 2), [16][17][18][19][20] verwandte cyclische und bicyclische Polyphosphorgerüste (V, VI) [21] und, im weiteren Sinne,d iverse Clusterkationen (IV) [22][23][24][25] sowie bicylische Systeme mit kationischen Substituenten. [25,26] Cyclische Tetraphospheniumkationen vergleichbar mit C wurden hingegen noch nicht beobachtet.Erst kürzlich entwickelten wir eine Synthesevorschrift für das Dichlorcyclotetraphosphan [ClP(m-PMes*)] 2 (1,M es* = 2,4,6-Tri-tert-butylphenyl), [27] das uns Untersuchungen der Reaktivität dieser wenig erforschten Substanzklasse ermçg-licht. [28,29] Hierbei fokussieren wir uns auf die selektive Funktionalisierung des P 4 -Gerüsts durch Substitution oder Abstraktion der Cl-Atome,i mG egensatz zur häufig verwendeten Methode der direkten Funktionalisierung von weißem Phosphor (P 4 )durch z. B. Lewis-Säure-Base-Systeme, Übergangsmetalle oder Singulettcarbene wie N-heterocyclische Carbene (NHCs) und cyclische Alkylaminocarbene (CAACs). [30][31][32][33] Während die Chemie von cyclischen Phosphanen mit kohlenstoff-oder stickstoffbasierten Substituenten gut untersucht ist, [34] gibt es keine Literaturberichte über die Reaktivität von halogensubstituierten cyclischen Te traphosphanen. Hier stellen wir daher Ergebnisse zur Reaktion von 1 mit der Lewis-Säure GaCl 3 vor.In Analogie zur Synthese cyclischer Dipniktadiazeniumsalze (C)w urde eine farblose Lçsung von 1·C 6 H 5 Fi nD ichlormethan bei tiefen Te mperaturen mit GaCl 3 umgesetzt, wobei eine sofortige tiefrote Färbung zu beobachten war.Insitu-31 P-NMR-Spektroskopie zeigte die intermediäre Bildung Schema 1. Ein formales Gleichgewicht zwischen monomerenI minopniktanen (A;Pn=P, As;X=(Pseudo-)Halogen) und cyclischen Dipniktadiazanen (B;P n=P, As, Sb, Bi)i nAbhängigkeitv om sterisch anspruchsvollen Rest Rermçglicht unterschiedliche Reaktionspfade, unter anderem die Bildung cyclischerD ipniktadiazeniumsalze (C; Pn = P, As, Sb, Bi).Schema 2. Strukturmotive in kationischen Phosphorringsystemen.

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Synthesis and structural characterization of the first donor-stabilized phosphanetriylphosphonium cation: [ArPP(PPh3)]+(Ar= 2,4,6-But 3C6H2)

Cited by 41 publications

References 17 publications

Heterobimetallic Cooperation Mediates the Transformation of White Phosphorus into Zwitterionic catena‐Phosphonium(+)diphosphenide(−) Ligands

Heterobimetallic Cooperation Mediates the Transformation of White Phosphorus into Zwitterionic catena‐Phosphonium(+)diphosphenide(−) Ligands

Aryldiazonium Salts as Nitrogen‐Based Lewis Acids: Facile Synthesis of Tuneable Azophosphonium Salts

Tieftemperatur‐Isolierung des bicyclischen Phosphinophosphoniumsalzes [Mes*₂P₄Cl][GaCl₄]

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Synthesis and structural characterization of the first donor-stabilized phosphanetriylphosphonium cation: [Ar*PP(PPh3)]+(Ar*= 2,4,6-But 3C6H2)

Cited by 41 publications

References 17 publications

Heterobimetallic Cooperation Mediates the Transformation of White Phosphorus into Zwitterionic catena‐Phosphonium(+)diphosphenide(−) Ligands

Heterobimetallic Cooperation Mediates the Transformation of White Phosphorus into Zwitterionic catena‐Phosphonium(+)diphosphenide(−) Ligands

Aryldiazonium Salts as Nitrogen‐Based Lewis Acids: Facile Synthesis of Tuneable Azophosphonium Salts

Tieftemperatur‐Isolierung des bicyclischen Phosphinophosphoniumsalzes [Mes*2P4Cl][GaCl4]

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Synthesis and structural characterization of the first donor-stabilized phosphanetriylphosphonium cation: [ArPP(PPh3)]+(Ar= 2,4,6-But 3C6H2)

Tieftemperatur‐Isolierung des bicyclischen Phosphinophosphoniumsalzes [Mes*₂P₄Cl][GaCl₄]