Cationic Diiodo‐Phosphoranides through Oxidative I<sub>2</sub> Addition to Tricyclic Phosphamethine Cyanines

Cicač-Hudi, Mario; Schlindwein, Simon H.; Feil, Christoph M.; Nieger, Martin; Gudat, Dietrich

doi:10.1002/zaac.201800264

Cited by 4 publications

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References 26 publications

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“…In the following time, a number of phosphoranido compounds were reported. Thereby, the addition of anions to phosphanes is a common approach for the generation of phosphoranide anions, especially (pseudo)halogenophosphoranides such as [P(CN) 3 X] − (X = Cl, Br, and I), [PCl 4 ] − , [PF 4 ] − , and [PR(CN) 2 X] (R = Me, Et, Ph, and C 6 F 5 ; X = Cl, Br, I, and NCS). − The addition of neutral donors to phosphanes facilitated the isolation of neutral, isolobal derivatives, such as [PBr 3 (PMe 3 )] and [PCl 2 R(NHC)] (R = Cl, Ph, and Me; NHC = N-heterocyclic carbene). − Even a small number of cationic compounds with the structural features of phosphoranides, such as [P(bipy) 2 ] 3+ and imidazoliumyl-substituted phosphorus compounds, were synthesized. − Deprotonation of phosphoranes represents another synthetic protocol for phosphoranide salts. − …”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 99%

“…13 C{1 H} NMR (CD 3 CN, 298 K, 151 MHz): 13.9 (d,3 J(C,P) = 4 Hz, 18 C, CH 2 CH 3 ), 32.0 (d, 3 J(C,P) = 5 Hz, 3 C, C(CH 3 ) 3 ), 40.0 (d, 2 J(C,P) = 6 Hz, 18 C, CH 2 ), 51.5 (d, 2 J(C,P) = 4 Hz, 1 C, C(CH 3 ) 3 ). CF 3 and CF 2 resonances were not observed.…”

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Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

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“…8,9 Even cationic species were synthesized, utilizing two imidazolium or imidazolinium based substituents. 10,11 [P(bipy) 2 ] 3+ represents another example of a cationic phosphoranide. 12 Phosphoranide salts are useful starting materials for the preparation of phosphoranidometal complexes, also called metallophosphoranes (for examples, see Figure 2).…”

Section: ■ Introductionmentioning

confidence: 99%

“…With the coordination of a neutral donor to a phosphane, the construction of a neutral compound can be realized. Suitable donors may be N-heterocyclic carbenes (NHC) or electron rich phosphanes. , Even cationic species were synthesized, utilizing two imidazolium or imidazolinium based substituents. , [P(bipy) 2 ] 3+ represents another example of a cationic phosphoranide …”

Section: Introductionmentioning

confidence: 99%

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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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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Cationic Diiodo‐Phosphoranides through Oxidative I₂ Addition to Tricyclic Phosphamethine Cyanines

Cited by 4 publications

References 26 publications

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

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

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

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Cationic Diiodo‐Phosphoranides through Oxidative I2 Addition to Tricyclic Phosphamethine Cyanines

Cited by 4 publications

References 26 publications

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties

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

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

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Cationic Diiodo‐Phosphoranides through Oxidative I₂ Addition to Tricyclic Phosphamethine Cyanines