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

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

“…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].…”

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

“…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].…”

N-Heterocyclic phosphenium cations: syntheses and cycloaddition reactions

“…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…”

The chemistry of cationic polyphosphorus cages – syntheses, structure and reactivity

“… 19 Phosphenium ions of type 6 + featuring one amino-substituent are borderline cases between both of the aforementioned types and are only scarcely investigated. Only a few fully characterized derivatives are reported to date bearing either (pseudo-) halogens 20 or sterically demanding aryl-moieties 21 as the second substituent R′ on phosphorus ( Fig. 3 ).…”

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

“…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].…”

N-Heterocyclic phosphenium cations: syntheses and cycloaddition reactions

“…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…”

The chemistry of cationic polyphosphorus cages – syntheses, structure and reactivity

“… 19 Phosphenium ions of type 6 + featuring one amino-substituent are borderline cases between both of the aforementioned types and are only scarcely investigated. Only a few fully characterized derivatives are reported to date bearing either (pseudo-) halogens 20 or sterically demanding aryl-moieties 21 as the second substituent R′ on phosphorus ( Fig. 3 ).…”

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

“…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].…”

N-Heterocyclic phosphenium cations: syntheses and cycloaddition reactions

“…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…”

The chemistry of cationic polyphosphorus cages – syntheses, structure and reactivity

“… 19 Phosphenium ions of type 6 + featuring one amino-substituent are borderline cases between both of the aforementioned types and are only scarcely investigated. Only a few fully characterized derivatives are reported to date bearing either (pseudo-) halogens 20 or sterically demanding aryl-moieties 21 as the second substituent R′ on phosphorus ( Fig. 3 ).…”