Tris(dialkylamino)benzylphosphoniumbromide - Phosphoniumsalze mit drei nahezu planar konfigurierten N-Atomen

Vogt, Hartmut; Wulff-Molder, Dirk; Ritschl, Friedrich Wilhelm; Mücke, Merlind; Skrabei, Ute; Meisel, M.

doi:10.1002/(sici)1521-3749(199906)625:6<1025::aid-zaac1025>3.0.co;2-v

Cited by 9 publications

(12 citation statements)

References 4 publications

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“…All three bisprotonated CDPs exhibit a strong inuence of charge delocalization as the reason for their extraordinary basicity: upon protonation the P-C bonds elongate from 1.606Å (4) and 1.618Å (1) to 1.799Å in 4$2HCl and 1.821Å in 1$2HBF 4 and 2$2HBF 4 , whilst the P-N bonds become shorter to average 1.62Å for pyrrolidine and 1.64Å for dimethylamine substituents. This complies with distances found in protonated phosphazenes 51 and phosphorus ylids 52 and proves the electron donating effect of the amino substituents. The P-N bonds to the tmg groups in 1$2HBF 4 exhibits with 1.58Å (1.66Å in 1) clearly double-bond character.…”

Section: Structural Featuressupporting

confidence: 86%

Design of non-ionic carbon superbases: second generation carbodiphosphoranes

et al. 2019

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Section: Structural Featuressupporting

confidence: 86%

Design of non-ionic carbon superbases: second generation carbodiphosphoranes

et al. 2019

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“…Synthesis of Some Benzyl-Substituted Amino Phosphonium Salts. The following general procedure 74,75 was used for the synthesis benzyl-substituted amino phosphonium salts of 44, 47, 49, 52, and 53. A solution of benzyl bromide in DMF (0.1 mol, 40 mL) was added to a phosphine compound solution in DMF (0.1 mol, 40 mL) at 0 °C.…”

Section: The Journal Of Organic Chemistrymentioning

confidence: 99%

“…The salt 44•CF 3 SO 3 H was collected as colorless crystals (0.82 g, 1.7 mmol, 89%), mp 153.3−154.2 °C.Ph-CHP(dma) 3 •CF 3 SO 3 H (47•CF 3 SO 3 H). From a tris-(dimethylamino)phosphine74,75 solution (4.1 g, 25 mmol) in 10.0 mL of DMF and a solution of benzyl bromide (5.4 g, 25 mmol) in 10 mL of DMF, 4.0 g (11.9 mmol, 48%) of 47•HBr was obtained, mp 232.4−233.8 °C (lit mp 229 °C). The triflate salt was prepared by mixing 0.80 g (2.4 mmol) of 47•HBr and 0.42 g (2.4 mmol) of CF 3 SO 3 Na in 2.0 mL of water to obtain 0.56 g (1.39 mmol, 58%) of 47•CF 3 SO 3 H, mp 189−190 °C: 1 H NMR (400 MHz, CD 3 CN) δ 7.47−7.28 (m, 5H), 3.81 (d, J P−H = 16.2 Hz, 2H), 2.65 (d, J = 9.8 Hz, 18H); 31 P NMR (162 MHz, CD 3 CN) δ 56.1.…”

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confidence: 99%

Experimental Basicities of Superbasic Phosphonium Ylides and Phosphazenes

et al. 2016

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Experimental basicities of some of the strongest superbases ever measured (phosphonium ylides) are reported, and by employing these compounds, the experimental self-consistent basicity scale of superbases in THF, reaching a pKα (estimate of pKa) of 35 and spanning more than 30 pKa units, has been compiled. Basicities of 47 compounds (around half of which are newly synthesized) are included. The solution basicity of the well-known t-Bu-N═P4(dma)9 phosphazene superbase is now rigorously linked to the scale. The compiled scale is a useful tool for further basicity studies in THF as well as in other solvents, in particular, in acetonitrile. A good correlation between basicities in THF and acetonitrile spanning 25 orders of magnitude gives access to experimentally supported very high (pKa > 40) basicities in acetonitrile, which cannot be directly measured. Analysis of structure-basicity trends is presented.

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“…Other structural data for cationic [(R 2 N) 3 PX] + systems (R = Me, Et, n Pr, n Bu) show that adoption of the C 3 conformation seems to be a general phenomenon of these salts. [19][20][21][22] In contrast, the series of compounds [p-(NO 2 )C 6 H 4 P(NR 2 ) 3 ]ClO 4 show a structural variation depending on the NR groups. 23 When NR = piperidine a C 3 conformation is observed, but when NR = morpholine the conformation changes to C s , which is consistent with the C s conformation seen for [O(C 2 H 4 ) 2 N] 3 PO.…”

Section: Introductionmentioning

confidence: 99%

The reactions of alkylamino substituted phosphines with I2 and (Ph2Se2I2)2: structural features of alkylamino phosphonium cations

et al. 2008

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The reactions of the tris-dialkylamino phosphines (Et2N)3P and (nPr2N)3P, and the pyrrolidinyl substituted phosphines (C4H8N)3P and tBuP(NC4H8)2, with I2 and (Ph2Se2I2)2, have been reported. The reactions with diiodine lead to the formation of [R3PI]I adducts, which are essentially ionic, but show a tendency to display long, soft-soft, II interactions in the solid state. The crystal structures of [(Et2N)3PI]I, (1), [(nPr2N)3PI]I, (2), and [(C4H8N)3PI]I, (3), have all been determined, and display II interactions varying between 3.5170(6) and 3.6389(14) A. The analogous reactions with (Ph2Se2I2)2 lead to the formation of phenylseleno-phosphonium salts, [R3PSePh]I. The structures of [(C4H8N)3PSePh]I, (6) and [(C4H8N)2tBuPSePh] I, (7), have been determined and do not display any soft-soft interactions between the selenium and iodine atoms. All of the phosphonium salts represent examples of structures containing tris-dialkylamino phosphine fragments which show no special nitrogen atom, i.e. all three nitrogen atoms are planar. This type of arrangement is usually observed when a C3 symmetric conformation is observed, (which is the case for 1 and 2), but not for the (C4H8N)3P adducts 3 and 6, where the conformation is closer to Cs, although the nitrogen atoms are still essentially planar. The P-N bonds in all the compounds reported herein are short, ranging between 1.599(12) A and 1.643(12) A, and are consistent with the previously reported short P-N bonds in phosphonium salts featuring tris-dialkylamino substituted phosphines.

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Tris(dialkylamino)benzylphosphoniumbromide - Phosphoniumsalze mit drei nahezu planar konfigurierten N-Atomen

Cited by 9 publications

References 4 publications

Design of non-ionic carbon superbases: second generation carbodiphosphoranes

Design of non-ionic carbon superbases: second generation carbodiphosphoranes

Experimental Basicities of Superbasic Phosphonium Ylides and Phosphazenes

The reactions of alkylamino substituted phosphines with I2 and (Ph2Se2I2)2: structural features of alkylamino phosphonium cations

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