Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates

Allefeld, Nadine; Neumann, Beate; Stammler, Hans‐Georg; Röschenthaler, Gerd‐Volker; Ignat’ev, Nikolai; Hoge, Berthold

doi:10.1002/chem.201402421

Cited by 11 publications

(17 citation statements)

References 28 publications

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“…The addition of a chloride ion to PCl(CN) 2 entails a shift of 123 ppm, and the addition of a cyanide ion to P(CN) 3 causes a shift of 101.5 ppm, to name but a few examples . The 31 P NMR chemical shifts of [PF 4 ] − [δ = 40.5 ppm], [P(C 2 F 5 ) 2 F 2 ] − [δ = 4 ppm], and [P(C 2 F 5 ) 3 F] − [δ = −34 ppm] nicely follow the tendency exhibited by the series [PX 4– n (CN) n ] − (X = Cl, Br). With increasing number of organosubstituents, the 31 P NMR resonances are shifted upfield …”

Section: Resultsmentioning

confidence: 67%

“…For this reason, electron withdrawing perfluoroorganyl groups seemed to be the systems of choice. Trifluoromethylphosphoranide salts were studied extensively by Röschenthaler and Shyshkov. , Cesium fluorotris(pentafluoroethyl)phosphoranide was NMR spectroscopically studied in an earlier work of our group, and we hypothesized that the difluorobis(pentafluoroethyl)phosphoranide ion would be a likely intermediate in the reaction of fluorobis(pentafluoroethyl)phosphane with the fluoride sources fluorotrimethyl[( Z )-pentafluoropropen-1-yl]phosphorane and Ishikawa’s reagent (Et 2 N-CF 2 -CHF-CF 3 ). − …”

Section: Introductionmentioning

confidence: 99%

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Difluorobis(pentafluoroethyl)phosphoranide: A Promising Building Block for Phosphoranidometal Complexes

et al. 2021

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Despite the fact that different metal tetrafluorophosphoranides, M [PF 4 ] (M = Cs, Ag, K), decompose readily, we successfully enhanced the stability of such species by the replacement of two fluorine atoms with electron withdrawing pentafluoroethyl groups. Thus, AgF adds to P(C 2 F 5 ) 2 F, yielding Ag[P(C 2 F 5 ) 2 F 2 ], which served as a starting material for the synthesis of mono-, bis-, and tris[difluorobis(pentafluoroethyl)phosphoranido]silver complexes. Addition of 2,2′-bipyridine allowed for the isolation of stable [Ag(bipy)-{P(C 2 F 5 ) 2 F 2 }], whereas the reaction with the chlorides [NMe 4 ]Cl and CoCl 2 afforded the bis-and trisphosphoranidoargentates, respectively. Altogether, the difluorobis(pentafluoroethyl)phosphoranido moiety serves as a novel, small, noncyclic phosphoranido ligand. It provided access to the first homoleptic phosphoranidometal complex, [Co(NCMe) 6 ][Ag{P(C 2 F 5 ) 2 F 2 } 3 ]•2MeCN, which itself features the unusual structural motif of an [AgX 3 ] 2− ion.

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Section: Resultsmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

Difluorobis(pentafluoroethyl)phosphoranide: A Promising Building Block for Phosphoranidometal Complexes

et al. 2021

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“…CsF adds to tris(pentafluoroethyl)phosphane ( 1) at low temperatures to furnish Cs[P(C 2 F 5 ) 3 F] (2 a), as previously reported by our group. [19] We now ascertained, that the compound immediately decomposes under formation of Cs[P(C 2 F 5 ) 2 F 2 ] (3 a) when warmed to room temperature (Scheme 3). Similar decomposition reactions have been observed for trifluoromethyl derivatives, which suffer a loss of difluorocarbene.…”

Section: Resultsmentioning

confidence: 99%

Triorganylphosphoranides: Realization of an Unusual Structural Motif Utilizing Electron Withdrawing Pentafluoroethyl Groups

et al. 2023

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Phosphoranides comprising three phosphorus carbon bonds are scarcely represented in the literature. We now utilized tris(pentafluoroethyl)phosphane, P(C2F5)3, and cyanobis(pentafluoroethyl)phosphane, P(C2F5)2(CN), featuring electron withdrawing pentafluoroethyl groups, to synthesize such compounds. Metal fluorides MF (M=Ag, Cs) add to P(C2F5)3 yielding respective M[P(C2F5)3F] salts. Those M[P(C2F5)3F] subsequently suffer a loss of C2F4, furnishing M[P(C2F5)2F2]. The cesium salt decomposes instantaneously when warmed to rt, whereas the silver salt decomposes slowly over several days at rt. Treatment of Ag[P(C2F5)3F] with 2,2’‐bipyridine facilitated the isolation and structural characterization of [Ag(bipy){P(C2F5)3F}]. With P(C2F5)2(CN), AgF reacts under substitution of the cyano group yielding P(C2F5)2F, rather than phosphoranide formation. However, [K(18‐crown‐6)]F adds to P(C2F5)2(CN) furnishing [K(18‐crown‐6)][P(C2F5)2(CN)F]. Its structural characterization was successful, despite its tendency to undergo an exchange of substituents, yielding [K(18‐crown‐6)][P(C2F5)2F2] and presumably [K(18‐crown‐6)][P(C2F5)2(CN)2]. The latter forms an equilibrium with [K(18‐crown‐6)]CN and P(C2F5)2(CN) which lies well on side of the phosphane and cyanide salt.

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“…Since strongly electron-withdrawing substituents should enhance the stability of phosphoranide salts, our attention was directed toward perfluoroalkyl groups. Previously, Röschenthaler and Shyshkov synthesized different trifluoromethylphosphoranide salts. − [K(18-crown-6)][P(CF 3 ) 3 F], for example, was obtained by the addition of KF to tris(trifluoromethyl)phosphane in the presence of 18-crown-6. , Since pentafluoroethylphosphanes exhibit a higher fluoride ion affinity and are safer to handle than trifluoromethylphosphanes, pentafluoroethyl derivatives were placed in the center of our research. , The addition of CsF to P(C 2 F 5 ) 3 yielded Cs[P(C 2 F 5 ) 3 F] at temperatures below −30 °C . The reaction of P(C 2 F 5 ) 2 F with Ishikawa’s reagent, Et 2 N–CF 2 –CHF–CF 3 , as well as fluorotrimethyl[( Z )-pentafluoropropen-1-yl]phosphorane, PMe 3 (CFCF–CF 3 )F, yielded [P(C 2 F 5 ) 2 F 2 ] − salts intermediately.…”

Section: Introductionmentioning

confidence: 99%

“…32,33 The addition of CsF to P(C 2 F 5 ) 3 yielded Cs[P(C 2 F 5 ) 3 F] at temperatures below −30 °C. 34 The reaction of P(C 2 F 5 ) 2 F with Ishikawa's reagent, Et 35,36 Reaction of P(C 2 F 5 ) 2 F with AgF led to the formation of Ag[P(C 2 F 5 ) 2 F 2 ], eventually. This silver salt served as a precursor for mono-, bis-, and trisphosphoranido silver complexes (Figure 1, top).…”

Section: ■ Introductionmentioning

confidence: 99%

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

et al. 2022

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In this contribution, we report on the “free” [P(C2F5)2F2]− ion and its ligand properties in transition metal complex chemistry. For this purpose, Ag[P(C2F5)2F2] was treated with [{(Et2N)3PN}3PNHC(CH3)3]Cl ([EtP4H]Cl) to yield [EtP4H][P(C2F5)2F2], featuring a weakly coordinating phosphazenium cation. Due to the weak interaction between the cation and anion, the [P(C2F5)2F2]− ion meets the so-called pseudo-gas-phase conditions. To determine the Tolman electronic parameter, [EtP4H][Ni(CO)3{P(C2F5)2F2}] was prepared from [EtP4H][P(C2F5)2F2] and [Ni(CO)4], facilitating the classification of the P(C2F5)2F2 moiety as a moderately π-acidic ligand. By treatment of [EtP4H][P(C2F5)2F2] with [AuCl(tht)], the neutral tetrahydrothiophene ligand was substituted by the phosphoranide ion, yielding [EtP4H][AuCl{P(C2F5)2F2}]. When Ag[P(C2F5)2F2] was treated with [AuCl(tht)], on the other hand, the chloride was substituted. Transmetalation reactions of this type proved to be an efficient transfer method of the P(C2F5)2F2 moiety, as further demonstrated by the reactions of Ag[P(C2F5)2F2] with [FeCl(CO)2Cp], [FeCl(CO)2Cp*], and [PdCl2(NCMe)2]. Surprisingly, P(C2F5)2F demonstrated fluorinating abilities toward [FeCl(CO)2Cp], [FeCl(CO)2Cp*], [AuCl(tht)], and [PdCl2(NCMe)2]. Apparently, fluorido transition metal complexes were generated in situ under the formation of P(C2F5)2Cl. The fluorido iron and palladium complexes transfer their fluoride ions onto P(C2F5)2F, yielding the respective phosphoranido complexes, featuring the P(C2F5)2F2 moiety.

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Synthesis and Reactivity of New Functionalized Perfluoroalkylfluorophosphates

Cited by 11 publications

References 28 publications

Difluorobis(pentafluoroethyl)phosphoranide: A Promising Building Block for Phosphoranidometal Complexes

Difluorobis(pentafluoroethyl)phosphoranide: A Promising Building Block for Phosphoranidometal Complexes

Triorganylphosphoranides: Realization of an Unusual Structural Motif Utilizing Electron Withdrawing Pentafluoroethyl Groups

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

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