Trimethylphosphine

Chemical Properties

Clear colorless liquid

Uses

Trimethylphosphine (PMe₃) is an electron-rich phosphine ligand used as a reagent in Mitsunobu reaction.
It can be used:

• In transformation of azides into carbamates; aziridines to azidoalcohols; and ketoximes to ketones with 2,2′-dipyridyl diselenide.
• In Aza-Wittig reaction;, C-H bond activation of imines; cross-coupling reactions.
• In the preparation of (cyanomethylene) trimethylphosphorane (CMMP) which is used as a reagent in Mitsunobu type reaction.
• As a reagent in the synthesis of ruthenium trimethylphosphine complexes, which in turn are used as catalysts for hydrogenation of CO₂ to formic acid.

Uses

Trimethylphosphine (PMe₃) solution is the suitable reagent used in the synthesis of Fe/Te cluster type complex, Fe₆Te₈(PMe₃)₆. It may be employed as a probe to investigate the acid sites in Y-zeolite. It may be used for the synthesis of hexakis(trimethylphosphine)tris-μ-methylene-diruthenium(III).

Uses

Trimethylphosphine is an electron-rich phosphine ligand used in the Mitsunobu reaction. It participates in the transformation of azides into carbamates, aziridines from azidoalcohols, iminophosphoranes and aza-Wittig reaction. This product is offered as a solution in 2-methyltetrahydrofuran for more convenient handling.

Definition

ChEBI: Trimethylphosphine is a tertiary phosphine.

General Description

Trimethylphosphine is the reagent used in Mitsunobu reaction. It participates in the transformation of azides into carbamates, aziridines from azidoalcohols, iminophosphoranes and aza-Wittig reaction. Electron diffraction study of trimethylphosphine has been reported.

reaction suitability

reagent type: ligand
reaction type: Mitsunobu Reaction
reagent type: ligand
reaction type: Wittig Reaction

Purification Methods

All operations should be carried out in an efficient fume cupboard because it is flammable, toxic and has a foul odor. Distil trimethylphosphine at atmospheric pressure in a stream of dry N2 (apparatus should be held together with springs to avoid loss of gas from increased pressure in the system) and the distillate run into a solution of AgI in aqueous KI whereby the silver complex [Me3PAgI]4 separates steadily. Filter off the complex, wash it with saturated aqueous KI solution, then H2O and dry it in a vacuum desiccator over P2O5. The dry complex is heated in a flask (in a stream of dry N2) in an oil bath at 140o, when pure Me3P distils off (bath temperature can be raised up to 260o). The vapour pressure of Me3P at 20o is 466mm and the b is 37.8o [Thomas & Eriks Inorg Synth IX 59 1967]. Alternatively, freshly distilled Me3P (6g) is shaken with a solution of AgI (13.2g, 1.1mol) in saturated aqueous KI solution (50mL) for 2hours. A white solid, not wetted with H2O, separates rapidly. It is collected, washed with the KI solution, H2O, and dried [Mann et al. J Chem Soc 1829 1937]. The silver complex is stable if kept dry in the dark, in which state it can be kept indefinitely. Me3P can be generated from the complex when required. Store it under N2 in a sealed container. It has been distilled in a vacuum line at -78o in vacuo and condensed at -96o [IR and NMR: Crosbie & Sheldrick J Inorg Nucl Chem 31 3684 1969]. The pK2 2 by NMR was 8.80 [Silver & Lutz J Am Chem Soc 83 786 1961, pK2 5 8.65: Henderson & Strueuli J Am Chem Soc 82 5791 1960].