A Crystalline Phosphenium Salt Featuring the Electron-Withdrawing 2,6-Bis(trifluoromethyl)phenyl Group

Dumitrescu, Anca; Schoeller, Wolfgang W.; Bourissou, Didier; Bertrand, Guy

doi:10.1002/1099-0682(200208)2002:8<1953::aid-ejic1953>3.0.co;2-y

Cited by 19 publications

(10 citation statements)

References 18 publications

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“…In low-coordinate phosphorus chemistry, the fluoromesityl and fluoroxyl groups have been employed in the synthesis of stable diphosphenes (ArP@PAr) [12,[20][21][22][23], iminophosphines ArP=NAr [24], phosphenium salts ðArPNR þ 2 Þ [25] and phosphides ArPR À [26]. Surprisingly, only a few phosphaalkenes containing the 2,4,6-(CF 3 )C 6 H 2 group have been described: ArP@CCl 2 , ArP@C(SiMe 3 )H, ArP@C(H)Ph [27] and ArP@CMe 2 [28].…”

Section: Introductionsupporting

confidence: 53%

Synthesis and characterisation of the platinum complexes [PtCl(CClPAr)(PPh3)2] and [PtCl(CClPAr′)(PPh3)2] as potential intermediates in the preparation of phosphaalkynes

Cornet

Dillon

Goeta

et al. 2005

Journal of Organometallic Chemistry

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Section: Introductionsupporting

confidence: 53%

Synthesis and characterisation of the platinum complexes [PtCl(CClPAr)(PPh3)2] and [PtCl(CClPAr′)(PPh3)2] as potential intermediates in the preparation of phosphaalkynes

Cornet

Dillon

Goeta

et al. 2005

Journal of Organometallic Chemistry

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“…This could be also be interpreted as an indication that inductive effects are relatively weak and that steric destabilisation of the fluoride complex is the dominant effect. However, the X-ray crystal structure of the [GaCl 4 ]salt of 7, 40 and the optimised gas-phase structure (Fig. 5) suggest that the explanation is not that simple.…”

Section: Inductive and Steric Stabilisationmentioning

confidence: 99%

How Lewis acidic is your cation? Putting phosphenium ions on the fluoride ion affinity scale

Slattery

Hussein

2012

Dalton Trans.

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The fluoride ion affinities (FIAs) of 33 phosphenium ions with a range of substituents were calculated using ab inito and DFT methods. The use of these FIA data as a measure of the Lewis acidities of phosphenium ions is described and the FIAs of the species studied here are compared to FIA data for more commonly encountered Lewis acids. Phosphenium ions are often stronger Lewis acids than neutral species, but in many cases are less Lewis acidic than highly electrophilic cations such as [Me(3)C](+) or [Me(3)Si](+). The impact of mesomeric, inductive and steric substituent effects on FIAs are discussed and related to the underlying electronic structures of different cation types. A comparison between the FIAs of known "free" phosphenium ions with those that are currently unknown and other highly electrophilic cations suggests that some diaryl- and dialkylphosphenium ions may yet be accessible under the right conditions.

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“…The metrical parameters of this compound were similar to those of other saturated NHP, but in this case, there was a P-O contact of 2.1850( 14 5), 1.784(6) A ˚)29 and by Bertrand in i Pr 2 NP(OTf)(2,6-(CF 3 ) 2 C 6 H 3 ) A ˚), which as late as 2002 was the "first covalent (trifluoromethansulfonate)phosphane to be structurally characterized." 30 Although the P-O length in 1a was longer than in the above examples, it was substantially shorter than those found in analogous saturated NHP compounds such as 1b (2.4210(18) A ˚,24 vide infra) and a diaminocyclohexane derivative by Kee (2.841(5) and 2.755(5) A ˚), 13 as well as two unsaturated NHP triflates reported by Gudat 8 that were clearly ionic in the solid state and had no cationanion contacts closer than the sum of van der Waal's radii. Moreover, the 31 P{ 1 H} NMR chemical shift of 1a (d P 172.9) was considerably upfield of that of its AlCl 4…”

Section: Synthesis and Structural Analysismentioning

confidence: 62%

N-Heterocyclic phosphenium cations: syntheses and cycloaddition reactions

et al. 2008

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A series of trifluoromethanesulfonate (OTf) salts of N-heterocyclic phospheniums (NHP) bearing phenyl (1a), para-methoxyphenyl (1b), 2,6-diisopropylphenyl (1c) and mesityl (1d) substituents is reported. The compounds are made by a modification to a literature procedure that improves the overall yields for and by 15 and 23%, respectively. Two unwanted side-products in the synthesis of , the diammonium salt, [(2,6-iPr-C6H3)N(H)2CH2CH2N(H)2(2,6-iPr-C6H3)]Cl2 (4) and the bisphosphine (2,6-iPr-C6H3)N(PCl2)CH2CH2N(PCl2)(2,6-iPr-C6H3) (5), are crystallographically characterized, as is the intermediate cyclic chlorophosphine, C1PN(4-OMe-C6H4)CH2CH2N(4-OMe-C6H4) (3b). The phenyl-substituted NHP is fully characterized, including by X-ray crystallography, for the first time; this compound contains a short P-O contact of 2.1850(14) A. Cycloaddition reactions of with 2,3-dimethyl-1,3-butadiene give the expected spirocyclic phospholeniums, 7,8-dimethyl-1,4-diaryl-1,4-diaza-5-phopshoniaspiro[4.4]non-7-ene, as their OTf salts (6a-d), while reactions with N,N'-dimesityl-1,4-diaza-1,3-butadiene give, except in the case of , which is too bulky to react, the aza analogues, 1,4-dimesityl-6,9-diaryl-1,4,6,9-tetraaza-5-phosphoniaspiro[4.4]non-2-ene (7a, 7b and 7d). The sterically congested is in thermal equilibrium with and free diazadiene, and undergoes a substitution reaction with 2,3-dimethyl-1,3-butadiene to give .

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A Crystalline Phosphenium Salt Featuring the Electron-Withdrawing 2,6-Bis(trifluoromethyl)phenyl Group

Cited by 19 publications

References 18 publications

Synthesis and characterisation of the platinum complexes [PtCl(CClPAr)(PPh3)2] and [PtCl(CClPAr′)(PPh3)2] as potential intermediates in the preparation of phosphaalkynes

Synthesis and characterisation of the platinum complexes [PtCl(CClPAr)(PPh3)2] and [PtCl(CClPAr′)(PPh3)2] as potential intermediates in the preparation of phosphaalkynes

How Lewis acidic is your cation? Putting phosphenium ions on the fluoride ion affinity scale

N-Heterocyclic phosphenium cations: syntheses and cycloaddition reactions

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