A Zwitterionic Gold(I) Diphenylphosphane Oxide Complex Stabilized by a Hard Pulling Lewis Acid and a Soft Pushing Lewis Base

Kather, Ralf; Lork, Enno; Beckmann, Jens

doi:10.1002/ejic.201700220

Cited by 3 publications

(7 citation statements)

References 52 publications

(36 reference statements)

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“…Specifically, the signal observed in the 31 P{ 1 H} NMR spectrum of 9 was observed at a position close to that of complex 5 (δ P 17.8) and was split into a septet by a scalar interaction with six fluorine atoms of B(C 6 F 5 ) 3 in ortho positions. The non‐decoupled 31 P NMR and 1 H NMR spectra confirmed the presence of two equivalent hydrogen atoms at phosphorus, whereas the position of the 11 B NMR resonance (δ B 0.7) corresponded with that reported for the similar adduct resulting from Ph 2 P(O)H [17a] . In contrast, BH 3 (1 equiv of THF solution) addition to 1O produced a complex mixture.…”

Section: Methodssupporting

confidence: 73%

A Stable Primary Phosphane Oxide and Its Heavier Congeners

Horký

Cı́sařová

Štěpnička

2020

Chemistry A European J

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(Ferrocenylmethyl)phosphane (1)o xidation with hydrogen peroxide, elemental sulfur and grey selenium produced (ferrocenylmethyl)phosphane oxide 1O,s ulfide 1S and selenide 1Se,r espectively,a st he first isolable primary phosphane chalcogenides lacking stericp rotection. At elevated temperatures, compound 1O disproportionated into 1 and (ferrocenylmethyl)phosphinic acid.I nr eactions with [(h 6-mes)RuCl 2 ] 2 , 1O underwent tautomerization into ap hosphanec omplex [(h 6-mes)RuCl 2 {FcCH 2 PH(OH)-kP}],w hereas 1S and 1Se lost their P-bound chalcogen atoms, giving rise to the phosphane complex [(h 6-mes)-RuCl 2 (FcCH 2 PH 2-kP)] (Fc = ferrocenyl, mes = mesitylene). No tautomerization was observed in the reactiono f1O with B(C 6 F 5) 3 ,w hich insteadp roduced aL ewis pair FcCH 2 P(O)H 2-B(C 6 F 5) 3 .P hosphane oxide 1O added to C=O bonds of aldehydes and ketonesa nd even to cumulenes PhNCE (E = Oa nd S). However,b oth PH hydrogens were only employed in the reactions with aldehydes and cyanates. Scheme1.Synthesis of P-chalcogenides 1E.

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Section: Methodssupporting

confidence: 73%

A Stable Primary Phosphane Oxide and Its Heavier Congeners

Horký

Cı́sařová

Štěpnička

2020

Chemistry A European J

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“…Ph2P(H)OB(C6F5)3 (153.5(1) pm). [63] This elongation is expected as the coordination number at oxygen increases. At this point the Lewis-acid coordination turned out to be a powerful method to structurally verify the phosphine oxide formation for all products 3), yet very rare push-pull main-group-phosphinidene complexes.…”

Section: Resultsmentioning

confidence: 88%

“…[52] Notably though, the Beckmann group has investigated the reactivity of the secondary phosphine oxide Ph2P(O)H towards B(C6F5)3 and in this case, the Lewis pair Ph2P(H)OB(C6F5)3 was obtained in good yield and characterized comprehensively including SC-XRD. [63] Additionally, 1: Mes Ter was reacted with GaCl3 and GaI3 in benzene, in order to verify the R-P(H)2O structural fragment as well. Ph2P(H)OB(C6F5)3 (153.5(1) pm).…”

Section: Resultsmentioning

confidence: 99%

On the ambiphilic character of phosphanylidenephosphoranes and manipulation of phosphinidenoid reactivity with Lewis acids

Dankert

Fischer

Hering‐Junghans

2022

Preprint

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Phosphanylidenephosphoranes of the type R−P(PR’3), also known as phospha-Wittig reagents, can be utilized in a variety of bond activation reactions pursuing their phosphinidenoid reactivity. In here, we thoroughly show that a facile PMe3 for H2O exchange gives access to various primary phosphine oxides of the general formula RP(H)2O (R = Mes*, MesTer, DipTer). The molecular structure of DipTerP(H)2O was determined and provided the first picture of such species in the solid state. However, phosphanylidenephosphoranes are described to be highly nucleophilic as well. We show that the attachment of main group Lewis acids such as GaCl3 and GaI3 to2 R−P(PMe3) yielded highly sensitive, yet stable coordination compounds [RP(GaX3)PMe3] (R = Mes*, DipTer) or [(RPPMe3)2GaCl2]GaCl4 (R = MesTer). In contrast to the free phosphanylidenephosphoranes, these species reacted differently with H2O which was demonstrated for [(Mes*PPMe3)GaI3]. Here the formation of the phosphinophosphonium cation [Mes*P(H)PMe3]+ and different anions was observed with combined NMR spectroscopic and SC-XRD (SC-XRD = single crystal diffraction analysis) studies. This work demonstrates that the ambiphilic character of phosphanylidenephosphoranes can be utilized to manipulate the reactivity of R−P(PMe3) towards water, giving primary phosphine oxides, whereas the Lewis acid adducts [(RPPMe3)GaX3] gave phosphino-phosphonium species.

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“…After work-up and recrystallization by gradually cooling a hot benzene solution to room temperature, X-ray . 63 This elongation is expected as the coordination number at oxygen increases. At this point the Lewis-acid coordination turned out to be a powerful method to structurally verify the phosphine oxide formation for all products 1:R (R = Mes*, Mes Ter) (Scheme 2).…”

Section: Papermentioning

confidence: 88%

“…52 Notably though, the Beckmann group has investigated the reactivity of the secondary phosphine oxide Ph 2 P(O)H towards B(C 6 F 5 ) 3 and in this case, the Lewis pair Ph 2 P(H)OB(C 6 F 5 ) 3 was obtained in good yield and characterized comprehensively including SC-XRD. 63 Additionally, 1: Mes Ter was reacted with GaCl 3 and GaI 3 in benzene. After work-up and recrystallization by gradually cooling a hot benzene solution to room temperature, X-ray .…”

Section: Papermentioning

confidence: 99%