594-09-2 Usage
Chemical Description
Trimethylphosphine is a tertiary phosphine with three methyl groups attached to the phosphorus atom.
Description
Trimethylphosphine, also known as PMe3, is an electron-rich phosphine ligand that is widely used in various chemical reactions and processes. It is known for its ability to participate in a range of reactions, including the Mitsunobu reaction, Aza-Wittig reaction, and C-H bond activation of imines, among others.
Uses
Used in Organic Synthesis:
Trimethylphosphine is used as a reagent in the Mitsunobu reaction for the transformation of azides into carbamates, aziridines to azidoalcohols, and ketoximes to ketones with 2,2′-dipyridyl diselenide. It is also used in the Aza-Wittig reaction, C-H bond activation of imines, and cross-coupling reactions.
Used in the Preparation of Reagents:
Trimethylphosphine is used in the preparation of (cyanomethylene)trimethylphosphorane (CMMP), which is also used as a reagent in Mitsunobu type reactions.
Used in Catalyst Synthesis:
Trimethylphosphine is used as a reagent in the synthesis of ruthenium trimethylphosphine complexes, which are used as catalysts for the hydrogenation of CO2 to formic acid.
Used in Inorganic Chemistry:
Trimethylphosphine solution is used in the synthesis of Fe/Te cluster type complex, Fe6Te8(PMe3)6. It may also be employed as a probe to investigate the acid sites in Y-zeolite and for the synthesis of hexakis(trimethylphosphine)tris-μ-methylene-diruthenium(III).
Trimethylphosphine is offered as a solution in 2-methyltetrahydrofuran for more convenient handling in various applications.
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].
Check Digit Verification of cas no
The CAS Registry Mumber 594-09-2 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 5,9 and 4 respectively; the second part has 2 digits, 0 and 9 respectively.
Calculate Digit Verification of CAS Registry Number 594-09:
(5*5)+(4*9)+(3*4)+(2*0)+(1*9)=82
82 % 10 = 2
So 594-09-2 is a valid CAS Registry Number.
InChI:InChI=1/C3H9P/c1-4(2)3/h1-3H3
594-09-2Relevant articles and documents
Shore, S. G.,Crist, J. L.,Lockman, B.,Long, J. R.,Coon, A. D.
, (1972)
Tetrakis(trimethylphosphine)nickel(0)
Avent, Anthony G.,Cloke, F. Geoffrey N.,Day, Jeremy P.,Seddon, Elaine A.,Seddon, Kenneth R.,Smedley, Stephen M.
, p. 535 - 542 (1988)
The title complex, , has been prepared by metal-vapour synthesis, and characterized by 1H, 13C, 31P, and 61Ni NMR spectroscopy and ultraviolet photoelectron (PE) spectroscopy.The 61Ni NMR spectrum exhibits a quintet 1J(NiP) 285 Hz>, and the t2 and e ionization energies occur at 5.60 and 6.52 eV, the lowest yet observed for a nickel(0) complex.
Reactions of a tungsten alkylidyne complex with mono-dentate phosphines: Thermodynamic and theoretical studies
Chen, Ping,Dougan, Brenda A.,Zhang, Xinhao,Wu, Yun-Dong,Xue, Zi-Ling
, p. 30 - 38 (2013)
Addition of mono-dentate phosphines PMe3 and PMe2Ph to the W(VI) alkyl alkylidyne complex W(CH2SiMe3) 3(≡CSiMe3) (1) is reversible, each reaching equilibrium. Thermodynamic studies of the equilibria have been conducted, giving ΔH° = -10.0(1.1) kcal/mol and ΔS° = -23(4) eu for the addition of PMe3 and ΔH°′ = -3.0 (0.7) kcal mol -1 and ΔS°′ = -6(3) eu for the addition of PMe 2Ph, indicating that the addition is exothermic. The experimental measurement allows a benchmarking study to select a proper DFT method to describe the current system. Of the DFT methods tested, M06 has demonstrated superior performance in calculating binding energy of a bimolecular reaction. The calculated reaction pathways show that W(CH2SiMe 3)3(≡CSiMe3) (1) reacts with PR3 to form W(CH2SiMe3)3(≡CSiMe3)(PR 3) (PR3 = PMe3, 3a; PMe2Ph, 3b), and the adduct then undergoes α-H migration to form W(CH2SiMe 3)2(=CHSiMe3)2(PR3) (4a, 4b). 4a and 4b are found to be thermodynamically and kinetically stable intermediates. The calculations also suggest a pathway in the formation of the alkyl alkylidene alkylidyne complex W(CH2SiMe3)- (=CHSiMe3)(≡CSiMe3)(PR3)2 (5a).
Thomas,Eriks
, p. 59,62 (1967)
Reactivity of (Pyridine-Diimine)Fe Alkyl Complexes with Carbon Dioxide
Lau, Ka-Cheong,Jordan, Richard F.
, p. 3658 - 3666 (2016)
The reaction of CO2 with (PDI)FeMe (1), (PDI)Fe(Me)PMe3 (1-PMe3) and [(PDI)FeMe][BPh4] (2, PDI = 2,6-(2,6-iPr2-C6H3-N=CMe)2-C5H3N) gen
Carmona, E.,Sanchez, L.
, p. 163 - 166 (1988)