Phosphorus-31 nuclear magnetic resonance studies on hydrobromides of substituted triarylphosphines and other derivatives

Grim, Samuel O.; Yankowsky, Anthony W.

doi:10.1021/jo00427a030

Cited by 51 publications

(24 citation statements)

References 3 publications

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“…The two trialkylphosphines give coupling constants that are significantly lower than the others. However, these data are consistent with those from previous studies (11)(12)(13); some selected data are presented in Fig. 4.…”

Section: (B) Nuclear Magnetic Resonance Data (I) 'J(p--h) In the Protsupporting

confidence: 92%

The basicity of phosphines

Allman¹,

Goel²

1982

Can. J. Chem.

213

112

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The basicities of the triarylphosphines P(4-XC6H4)3 (X = Cl, F, H, CH3, CH3O, (CH3)2N), P(3-CH3C6H4)3, and P(2-CH3C6H7)3 as well as the trialkylphosphines P(t-Bu)3 and PCy3 have been measured by the nitromethane titration method. The range of basicity available by aryl substitution is very large, being pKa = 8.65 for X = (CH3)2N to 1.03 for X = Cl. The most basic phosphine is P(t-Bu)3 whose pKa = 11.40. The measured basicities correlate well with σp, [Formula: see text], and ν as well as with the lone pair ionisation potentials of the triarylphosphines. Generally the 1H, 31P, and 13C nmr spectral parameters of the free and protonated phosphines do not correlate well with pKa.

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Section: (B) Nuclear Magnetic Resonance Data (I) 'J(p--h) In the Protsupporting

confidence: 92%

The basicity of phosphines

Allman¹,

Goel²

1982

Can. J. Chem.

213

112

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“…500 Hz in the coupled spectrum. This large coupling is good proof of the occurrence of a protonated phosphine (31). We interpret this spectrum in terms of the formation, in the metal-rich mixtures, -of the comschematically in 1 (in which a pyramidal M(PA),PB kernel is likely (see above)).…”

Section: Complexes With Polydentate Phosphinessupporting

confidence: 52%

A ³¹P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the ³¹P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides

Dean¹,

Phillips²,

Polensek³

1981

Can. J. Chem.

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31P nmr has been used to show that, in MeNO2, M(SbF6)2 (M = Sn or Pb) forms 1:1 complexes with Ph2P(CH2)2PPh2, PhP[(CH2)2PPh2]2, MeC(CH2PPh2)3, [Formula: see text][Formula: see text]P[(CH2)2PPh2]3, and Ph2P[(CH2)2PPh]2(CH2)2PPh2. The phosphonium ligands are formed in situ. Spectra characteristics of slow inter- and intramolecular exchange were obtained in all cases except, perhaps, those involving the last two ligands, which may be involved in rapid intramolecular exchange. For the first five ligands, the maximum denticity is achieved and unambiguous one-bond M(II)—31P (M = 117/119Sn or 207Pb) coupling constants are reported and discussed. In the presence of M(SbF6)2 (M = Sn or Pb). PPh3 is protonated in MeNO2, while in acetone Sn(SbF6)2 forms a 1:1 complex with PPh3 which appears to be solvent-inserted, [Sn—O—CMe2PPh3]2+.Reduced temperature 31P nmr spectroscopy has allowed the detection of 1:2 and 1:3 (M:L) complexes of OPPh3, and 1:1 complexes of Ph2P(O)(CH2)2P(O)Ph2, PhP(O)[(CH2)2P(O)Ph2]2, and (O)P[(CH2)2P(O)Ph2]3, with both tin(II) and lead(II). The 1:1 complexes with polydentate ligands are isolable; nmr shows that the maximum denticity occurs except with the last ligand which behaves in a tridentate manner. Several two-bond M—O—P coupling constants have been obtained. Also, the changes which complexation produces in the P—P couplings are compared with changes produced in the analogous phosphine complexes.The synthesis and characterization of Ph2P(E)[(CH2)2P(E)Ph]2(CH2)2P(E)Ph2 (E = S or Se) and (Se)P[(CH2)2P(Se)Ph2]3 are reported. The 31P nmr spectra of these compounds are compared with those of the parent tetraphosphines and other members of the corresponding tetraoxide–tetrachalcogenide series.

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“…A procedure analogous to that for 12a but using HPotol 2 (0.429 g, 2.00 mmol) [30] and 11 (0.645 g, 1.01 mmol) gave 12c as a white solid (0.786 g, 0.863 mmol, 86%), m.p. 94-96°C.…”

Section: 15mentioning

confidence: 99%

Monophosphine and diphosphine ligands for diplatinum polyynediyl complexes: Efficient syntheses of new functionality-containing systems and model compounds

Quadras

Stähl

Zhuravlev

et al. 2007

Journal of Organometallic Chemistry

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Phosphorus-31 nuclear magnetic resonance studies on hydrobromides of substituted triarylphosphines and other derivatives

Cited by 51 publications

References 3 publications

The basicity of phosphines

The basicity of phosphines

A ³¹P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the ³¹P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides

Monophosphine and diphosphine ligands for diplatinum polyynediyl complexes: Efficient syntheses of new functionality-containing systems and model compounds

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Phosphorus-31 nuclear magnetic resonance studies on hydrobromides of substituted triarylphosphines and other derivatives

Cited by 51 publications

References 3 publications

The basicity of phosphines

The basicity of phosphines

A 31P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the 31P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides

Monophosphine and diphosphine ligands for diplatinum polyynediyl complexes: Efficient syntheses of new functionality-containing systems and model compounds

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A ³¹P nmr spectroscopic study of complexation of tin(II) and lead(II) by some phosphines, phosphine oxides, and related ligands, with the ³¹P nuclear magnetic resonance spectra of two tetratertiary phosphine tetraoxides and the analogous tetra-sulfides and -selenides