Phosphoranes.  3.  New tris(trifluoromethyl)phosphoranes (CF3)3PXY with monofunctional [F, Cl, N(CH3)2, OCH3, SCH3 OSi(CH3)3] substituents

THE, K. I.; Cavell, Ronald G.

doi:10.1021/ic50164a040

Cited by 15 publications

(2 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the compounds in which CF3 is the most electronegative substituent (Y = OCH3, SCH3, N(CH3)2) the proposed structures are also in keeping with the electronegativity rule21 and 2/PF values are consistent with previously suggested rules. 22,23,[25][26][27] Also in this series the chemical shift values exhibit a regular trend with those values arising from axial CF3 groups consistently falling to low field of the equatorial CF3 group signals. Chemical shift trends are not always dependable22,23,25-27 and the present trend is probably coincidental.…”

Section: Resultsmentioning

confidence: 55%

Phosphoranes. 5. Chemistry and stereochemistry of tetraalkylphosphoranes, CH3(CF3)3PX, with one methyl group and monofunctional [F, Cl, OCH3, SCH3, N(CH3)2] substituents

THE¹,

Cavell²

1977

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

Methylation of (CF3)3PF2 with tetramethyltin or (CF3)3PX2 (X = F, Cl) with tetramethyllead gave the tetraalkylphosphoranes, CH3(CF3)3PX, which, according to the NMR spectra, are best formulated as five-coordinate phosphoranes rather than isomeric phosphonium salts. NMR (19F, 31P, and 13C) spectroscopic studies at low temperatures consistently indicate that the halogen, F or Cl, occupies an axial position in an assumed trigonal-bipyramidal structure and that the methyl group resides in the trigonal plane giving a ground-state structure with one axial and two equatorial CF3 groups. Metathetical substitution of the halogen with groups Y (Y = OCH3, SCH3, N(CH3)2) using (CH3)3SiY reagents or (CH3)2NH gives the derivative phosphoranes CH3(CF3)3PY which, according to NMR (19F, 3IP) spectroscopic studies at appropriate temperatures, have ground-state structures in which Y and CH3 reside in the equatorial plane of the trigonal bipyramid placing one CF3 group in an equatorial position and two CF3 groups in axial positions. In general CF3 environments are averaged by an exchange process with barriers, as indicated by coalescence temperatures, decreasing in the order N(CH3)2 > SCH3 > OCH3 >> F > Cl. The different CF3 environments in CH3(CF3)3PN(CH3)2 are observed at normal room temperatures. Other mass, NMR, and infrared spectroscopic data are reported as well as the hydrolytic behavior of the phosphoranes.

show abstract

Section: Resultsmentioning

confidence: 55%

Phosphoranes. 5. Chemistry and stereochemistry of tetraalkylphosphoranes, CH3(CF3)3PX, with one methyl group and monofunctional [F, Cl, OCH3, SCH3, N(CH3)2] substituents

THE¹,

Cavell²

1977

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

show abstract

“…31P spectra were recorded at 36. 4 MHz with a Bruker HFX-90-Nicolet 1085 spec- 14.0 0.8 0 Solvent. Unless otherwise noted neutral water was used for hydrolysis.…”

Section: Methodsmentioning

confidence: 99%

Phosphoranes. 7. Chemistry and stereochemistry of monofunctionally substituted tetraalkylphosphoranes, (CH3)2(CF3)2PY [Y = F, Cl, OCH3, SCH3, and N(CH3)2], including a second example of individual nonequivalence of fluorine atoms in a trifluoromethyl group attached to phosphorus

Cavell¹,

THE²

1978

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

ChemInform Abstract: PHOSPHORANES. 3. NEW TRIS(TRIFLUOROMETHYL)PHOSPHORANES (CF3)3PXY WITH MONOFUNCTIONAL (F, CL, N(CH3)2, OCH3, SCH3 OSI(CH3)3) SUBSTITUENTS

THE¹,

Cavell²

1976

Chemischer Informationsdienst

View full text Add to dashboard Cite

Phosphoranes. 3. New tris(trifluoromethyl)phosphoranes (CF3)3PXY with monofunctional [F, Cl, N(CH3)2, OCH3, SCH3 OSi(CH3)3] substituents

Cited by 15 publications

References 5 publications

Phosphoranes. 5. Chemistry and stereochemistry of tetraalkylphosphoranes, CH3(CF3)3PX, with one methyl group and monofunctional [F, Cl, OCH3, SCH3, N(CH3)2] substituents

Phosphoranes. 5. Chemistry and stereochemistry of tetraalkylphosphoranes, CH3(CF3)3PX, with one methyl group and monofunctional [F, Cl, OCH3, SCH3, N(CH3)2] substituents

Phosphoranes. 7. Chemistry and stereochemistry of monofunctionally substituted tetraalkylphosphoranes, (CH3)2(CF3)2PY [Y = F, Cl, OCH3, SCH3, and N(CH3)2], including a second example of individual nonequivalence of fluorine atoms in a trifluoromethyl group attached to phosphorus

ChemInform Abstract: PHOSPHORANES. 3. NEW TRIS(TRIFLUOROMETHYL)PHOSPHORANES (CF3)3PXY WITH MONOFUNCTIONAL (F, CL, N(CH3)2, OCH3, SCH3 OSI(CH3)3) SUBSTITUENTS

Contact Info

Product

Resources

About