594-09-2

Basic information

• Product Name: Trimethylphosphine
• Synonyms: (CH3)3P;Trimethyl-phosphane;Trimethylphosphorus;TRIMETHYLPHOSPHINE;PHOSPHORUS TRIMETHYL;Trimethylphosphine solution;Trimethylphosphineminampouled;TrimethylphosphineSureSealbottlecolorlessliquid
• CAS NO: 594-09-2
• Molecular Formula: C₃H₉P
• Molecular Weight: 76.08
• EINECS: 209-823-1
• Product Categories: Catalysis and Inorganic Chemistry;Phosphine Ligands;Phosphorus Compounds;organophosphorus ligand
• Mol File: 594-09-2.mol
• Article Data: 67

Chemical Properties

• Melting Point: −86 °C(lit.)
• Boiling Point: 38-40 °C(lit.)
• Flash Point: −4 °F
• Appearance: colorless/liquid
• Density: 0.872 g/mL at 25 °C
• Vapor Pressure: 7.24 psi ( 20 °C)
• Refractive Index: n20/D 1.428(lit.)
• Storage Temp.: 2-8°C
• Water Solubility: Soluble in water.
• Sensitive: Air & Moisture Sensitive
• BRN: 969138
• CAS DataBase Reference: Trimethylphosphine(CAS DataBase Reference)
• NIST Chemistry Reference: Trimethylphosphine(594-09-2)
• EPA Substance Registry System: Trimethylphosphine(594-09-2)

Safety Data

• Hazard Codes: F,Xn,Xi
• Statements: 11-36/37/38-67-65-63-48/20-38-17-40-36/37-19
• Safety Statements: 9-16-26-36/37/39-62-36/37-7/9-33
• RIDADR: UN 1993 3/PG 2
• WGK Germany: 3
• F: 10-13-23
• HazardClass: 4.2
• PackingGroup: I
• Hazardous Substances Data: 594-09-2(Hazardous Substances Data)

Usage

Chemical Description

Trimethylphosphine is a tertiary phosphine with three methyl groups attached to the phosphorus atom.

Chemical Properties

Clear colorless liquid

Uses

Different sources of media describe the Uses of 594-09-2 differently. You can refer to the following data:
1. 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.
2. 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).
3. 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.

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.

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].

InChI:InChI=1/C3H9P/c1-4(2)3/h1-3H3

Synthetic route

Re(C5H5)(CO)(NO)(CH3)(P(CH3)3)2 → (η5-C5H5)(CO)(NO)ReCH3 + trimethylphosphane (594-09-2)

Conditions	Yield
In acetone for 1 h; evapd. slowly under vacuo;	A 98% B n/a
In [(2)H6]acetone at room temp. for 1 day;
In tetrahydrofuran Kinetics; monitored by UV;

methyl isocyanate (593-75-9, 685498-28-6) + (η(5)-C5Me5)Co(PMe3)2 → {(C5(CH3)5)Co(CNCH3)(P(CH3)3)} + trimethylphosphane (594-09-2)

Conditions	Yield
In diethyl ether under Ar, reaction temp.: -78°C, warmed to room temp.; removal of solvent, extn. (pentane), brought to dryness in vac., stored at -78°C for 2 days;	A 95% B n/a

methylene chloride (74-87-3) + phosphan (7803-51-2) → methylphosphine (593-54-4) + dimethylphosphane (676-59-5) + chloro-tetramethyl-phosphorane (880343-42-0) + trimethylphosphane (594-09-2)

Conditions	Yield
With potassium hydroxide; PTK In toluene at 15℃; for 18h;	A 4% B 92% C 4 g D 2%

methylenetriphenylphosphorane-(4,5-diethyl-2,5-dihydro-2,2,3-trimethyl-1-phenyl-1,2,5-phosphasilaborole) (114130-53-9) → dimeric (P-B)(2)-4,5-diethyl-1,2,5,6-tetrahydro-2,2,3-trimethyl-1-phenyl-1,2,5-phosphasilaborine * toluene (114182-21-7) + trimethylphosphane (594-09-2)

Conditions	Yield
With toluene In toluene Ar atmosphere, refluxing (3 h); sublimation of PMe3, recrystn. of B-complex (hot toluene), washing (toluene), drying (0.001 Torr); elem. anal.;	A 84% B 92%

(η5-C5Me5)(PMe3)2Ru(CH2SiMe3) (87640-52-6) + Triethoxysilane (998-30-1) → tetramethylsilane (75-76-3) + (η5-C5Me5)(PMe3)ruthenium{Si(OEt)3}2H + trimethylphosphane (594-09-2)

Conditions	Yield
In inert atmosphere, heating of Ru-complex with HSi(OEt)3 (80°C, 12 h, closed vessel), briefly pumping to remove PMe3, continued heating (80°C, 6 h).; Evapn. in vac. gives a waxy solid, recrystn. (acetone), elem. anal.;	A n/a B 92% C n/a

(bis(diisopropylamino)phosphanyl)diazomethane, lithium salt (113533-26-9) + rhodium(trimethylphosphine)4Cl (70525-09-6, 92670-96-7) → 5-bis(trimethylphosphine)rhoda-4-bis(diisopropylamino)phospha-1-n-butyl-Δ2-pyrazoline (116405-38-0) + trimethylphosphane (594-09-2)

Conditions	Yield
With n-C4H9Li byproducts: LiCl; Excess of n-Buli.;	A 90% B n/a

cis-HRh(COCH3)(P(CH3)3)3Cl (82555-25-7) → RhCl(CO)(PMe3)2 (36713-95-8, 133577-23-8, 22710-50-5) + [Rh(trimethylphosphine)3]Cl (36103-64-7) + methane (34557-54-5) + acetaldehyde (75-07-0) + trimethylphosphane (594-09-2)

Conditions	Yield
Rh complex heated at 90°C for 2 h; collection of the volatile products under high vaccum;	A 13% B 80% C 13% D 87% E 19%
In benzene-d6 soln. of Rh complex in benzene-d6 heated at 70°C for 2 h;	A 54% B 15% C 51% D 14% E 50%

(cyclopentadienyl)bis(trimethylphosphine)cobalt + dimethylfumarate (624-49-7) → {cyclopentadienyl(trimethylphosphane)2(fumaric acid dimethylester)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In diethyl ether addn. of fumaric acid dimethylester to the Co compd. in ether under Ar and stirring at room temp. for 30 min; evapn. (vac.), chromy. on Al2O3, elution with ether-pentane, concn. (vac.), filtn., washing with pentane and drying (vac.); elem. anal.;	A 85% B n/a

(cyclopentadienyl)bis(trimethylphosphine)cobalt + acrylic acid methyl ester (292638-85-8) → {cyclopentadienyl(trimethylphosphane)(acrylic acid methylester)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In hexane addn. of acrylic acid methylester to the Co compd. in hexane under Ar and stirring at room temp. for 30 min; evapn. (vac.), dissolving in ether, chromy. on Al2O3, elution with ether-hexane, concn., cooling to -78°C, filtn., washing with cold pentane and drying (vac.); elem. anal.;	A 85% B n/a
In diethyl ether addn. of acrylic acid methylester to the Co compd. in ether under Ar and stirring at room temp. for 30 min; evapn. (vac.), dissolving in ether, chromy. on Al2O3, elution with ether-hexane, concn., cooling to -78°C, filtn., washing with cold pentane and drying (vac.); elem. anal.;	A 85% B n/a

(cyclopentadienyl)bis(trimethylphosphine)cobalt + Benzyl isocyanide (88333-03-3, 10340-91-7) → (η(5)-C5H5)Co(PMe3)(CNCH2Ph) + trimethylphosphane (594-09-2)

Conditions	Yield
In benzene under Ar, stirred for a few minutes at room temp.; removal of solvent in vac., extn. (pentane), cooling to -78°C; elem. anal.;	A 85% B n/a

(η2-1,2-diphenyl-1-cyclopropene)(trimethylphosphane)zirconocene (133911-64-5) → 1,1-bis(η5-cyclopentadienyl)-2,3-diphenyl-1-(trimethylphosphane)-1-zirconacyclobut-2-ene (133911-65-6) + 1,1-bis(η5-cyclopentadienyl)-2,3-diphenyl-1-zirconacyclobut-2-ene (133911-66-7) + trimethylphosphane (594-09-2)

Conditions	Yield
In tetrahydrofuran-d8 (Ar), -100°C; (31)P-NMR;	A 84% B 0% C 16%

bis(trimethylphosphine)(eta.5-indenyl)cobalt + acrylic acid methyl ester (292638-85-8) → {indenyl(trimethylphosphane)(acrylic acid methylester)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In hexane addn. of acrylic acid methylester to the Co compd. in hexane under Ar and stirring at room temp. for 30 min; evapn. (vac.), dissolving in ether, chromy. on Al2O3, elution with ether-hexane, concn., cooling to -78°C, filtn., washing with cold pentane and drying (vac.); elem. anal.;	A 83% B n/a
In diethyl ether addn. of acrylic acid methylester to the Co compd. in ether under Ar and stirring at room temp. for 30 min; evapn. (vac.), dissolving in ether, chromy. on Al2O3, elution with ether-hexane, concn., cooling to -78°C, filtn., washing with cold pentane and drying (vac.); elem. anal.;	A 83% B n/a

tetrakis(trimethylphosphine)platinum(0) (33937-27-8) + Benzo[b]thiophene (95-15-8) → [(CH3)3P]2PtC8SH6 (202662-81-5) + trimethylphosphane (594-09-2)

Conditions	Yield
In toluene reflux; elem. anal.;	A 83% B n/a

carbon disulfide (75-15-0) + tetrakis(trimethylphosphine)nickel(0) (28069-69-4) → [nickel(0)(trimethylphosphine)3(η2-SCS)] + trimethylphosphane (594-09-2)

Conditions	Yield
In diethyl ether at 0 - 20℃; for 24h; Inert atmosphere; Schlenk technique;	A 81% B n/a

trans-(2,4,6-trimethylphenyl)chlorobis(trimethylphosphine)nickel(II) + sodium cyclopentadienide → {(η5-C5H5)Ni(2,4,6-C6H2Me3)(PMe3)} + trimethylphosphane (594-09-2)

Conditions	Yield
In not given byproducts: NaCl; N2 atmosphere; react. of Ni-complex with excess of NaCp (1.5 equiv) at 20°C for 12 h; elem. anal.;	A 80% B n/a

trans-{Ni(2,4,6-C6H2Me3)Br(PMe3)2} + sodium cyclopentadienide → {(η5-C5H5)Ni(2,4,6-C6H2Me3)(PMe3)} + trimethylphosphane (594-09-2)

Conditions	Yield
In not given byproducts: NaBr; N2 atmosphere; react. of Ni-complex with excess of NaCp (1.5 equiv) at 20°C for 12 h; elem. anal.;	A 80% B n/a

(cyclopentadienyl)bis(trimethylphosphine)cobalt + dimethylfumarate (624-49-7) → {indenyl(trimethylphosphane)2(fumaric acid dimethylester)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In diethyl ether addn. of fumaric acid dimethylester to the Co compd. in ether under Ar and stirring at room temp. for 30 min; evapn. (vac.), chromy. on Al2O3, elution with ether-pentane, concn. (vac.), filtn., washing with pentane and drying (vac.); elem. anal.;	A 80% B n/a

(cyclopentadienyl)bis(trimethylphosphine)cobalt + dimethylfumarate (624-49-7) → {trifluoromethylcyclopentadienyl(trimethylphosphane)2(fumaric acid dimethylester)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In diethyl ether addn. of fumaric acid dimethylester to the Co compd. in ether under Ar and stirring at room temp. for 30 min; evapn. (vac.), chromy. on Al2O3, elution with ether-pentane, concn. (vac.), filtn., washing with pentane and drying (vac.); elem. anal.;	A 78% B n/a

(η5-C5Me5)(PMe3)2Ru(CH2SiMe3) (87640-52-6) + diphenylsilyl chloride (1631-83-0) → tetramethylsilane (75-76-3) + (η5-C5Me5)(PMe3)ruthenium{Si(phenyl)2Cl}2H + trimethylphosphane (594-09-2)

Conditions	Yield
In inert atmosphere, heating of Ru-complex with HSi(Ph2Cl)3 (110°C, 16 h, closed vessel, stirring), periodic pumping to remove PMe3.; Cooling to room temp., addn. of pentane, cooling (-78°C, 6 h), filtn. of pale yellow crystals, washing (pentane, -78°C), drying in vac, elem. anal.;	A n/a B 78% C n/a

chlorodimethyloxobis(trimethylphosphine)rhenium(V) + 1,2-bis(dimethylphosphanyl)ethane (23936-60-9) → chlorodimethyloxo(bis(dimethylphosphino)ethane)rhenium(V) + trimethylphosphane (594-09-2)

Conditions	Yield
In toluene N2 or Ar atmosphere of vac.; stirring (1 h); filtn., concn. (vac.), cooling (-20°C); elem. anal.;	A 76% B n/a

allylmagnesium bromide (1730-25-2) → (η5-pentamethylcyclopentadienyl)(PMe3)Fe(C3H5) + trimethylphosphane (594-09-2)

Conditions	Yield
In tetrahydrofuran; diethyl ether inert atmosphere; -78°C, then room temp., stirring 15 min.; evapn. (vac.), drying, extn. (petroleum ether), partial evapn. of filtrate, crystn. (-78°C), collection (filtration), drying (vac.); elem. anal.;	A 76% B n/a

trans-MoCl(NO)(PMe3)4 (119998-04-8) → MoCl(η3-S2CPMe3)(NO)(PMe3)2 (119998-14-0) + trimethylphosphane (594-09-2)

Conditions	Yield
With CS2 In tetrahydrofuran Ar or N2 atmosphere; addn. of 1.4 equiv of CS2 to a soln. of Mo-complex, stirring (24 h at room temp.), pptn.; collection (filtration), washing (Et2O), crystn. (CHCl3), -30°C;	A 75% B n/a

{AgNO3(trimethylphosphine)} + thiourea (17356-08-0) → trimethylphosphane (594-09-2)

Conditions	Yield
In water heating an aq. soln. of the Ag compound with a concd. soln. of thiourea with N2 bubbling through the soln.;	75%

bis(trimethylphosphine)(η5-trifluoromethylcyclopentadienyl)cobalt + acrylic acid methyl ester (292638-85-8) → {trifluoromethylcyclopentadienyl(trimethylphosphane)(acrylic acid methylester)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In hexane addn. of acrylic acid methylester to the Co compd. in hexane under Ar and stirring at room temp. for 30 min; evapn. (vac.), dissolving in ether, chromy. on Al2O3, elution with ether-hexane, concn., cooling to -78°C, filtn., washing with cold pentane and drying (vac.); elem. anal.;	A 73% B n/a
In diethyl ether addn. of acrylic acid methylester to the Co compd. in ether under Ar and stirring at room temp. for 30 min; evapn. (vac.), dissolving in ether, chromy. on Al2O3, elution with ether-hexane, concn., cooling to -78°C, filtn., washing with cold pentane and drying (vac.); elem. anal.;	A 73% B n/a

bis(trimethylphosphine)(eta.5-indenyl)cobalt + acrylonitrile (107-13-1) → {indenyl(trimethylphosphane)2(acrylonitrile)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In diethyl ether addn. of acrylonitrile to the Co compd. in ether under Ar and stirring at room temp. for 1 h; evapn. (vac.), dissolving in ether-hexane, chromy. on Al2O3, elution with ether-hexane, concn., cooling to -78°C, filtn., washing with pentane and drying (vac.); elem. anal.; exo-endo-mixture, identified by (1)H-NMR;	A 73% B n/a

(cyclopentadienyl)bis(trimethylphosphine)cobalt + acrylonitrile (107-13-1) → {cyclopentadienyl(trimethylphosphane)2(acrylonitrile)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In diethyl ether addn. of acrylonitrile to the Co compd. in ether under Ar and stirring at room temp. for 1 h; evapn. (vac.), dissolving in ether-hexane, chromy. on Al2O3, elution with ether-hexane, concn., cooling to -78°C, filtn., washing with pentane and drying (vac.); elem. anal.; exo-endo-mixture, identified by (1)H- and (13)C-NMR;	A 72% B n/a

tetrakis(trimethylphosphine)nickel(0) (28069-69-4) + phenyl isothiocyanate (103-72-0) → [nickel(trimethylphosphine)3(η2-SCNPh)] + trimethylphosphane (594-09-2)

Conditions	Yield
In diethyl ether at 0 - 20℃; for 24h; Inert atmosphere; Schlenk technique;	A 72% B n/a

MoCl2(CO)2{P(CH3)3}3 (83828-53-9) + potassium isopropylxanthate (140-92-1) → Mo(η3-(S,S',C)S2CO-i-Pr)2(CO)(trimethylphosphine)2 (125841-34-1) + trimethylphosphane (594-09-2)

Conditions	Yield
In tetrahydrofuran byproducts: CO, KCl; N2 or Ar atmosphere; stirring (2 h, room temp.); evapn. (vac.), extn. (petroleum ether/Et2O 1:1), centrifugation and cooling (-35°C); elem. anal.;	A 70% B n/a

maleic anhydride (108-31-6) + (cyclopentadienyl)bis(trimethylphosphine)cobalt → {cyclopentadienyl(trimethylphosphane)2(maleic anhydride)cobalt} + trimethylphosphane (594-09-2)

Conditions	Yield
In benzene addn. of maleic anhydride to the Co compd. in benzene under Ar and stirring at room temp. for 30 min; evapn. (vac.), washing with hexane, recrystn. from acetone-hexane, filtn., washing with ether and pentane and drying (vac.); elem. anal.;	A 70% B n/a

trans-{W(ethylene)2(P(CH3)3)4} (84879-23-2) → {WH(OOCCHCH2)(C2H4)(P(CH3)3)2}2*0.5(C2H5)2O (122214-24-8) + trimethylphosphane (594-09-2)

Conditions	Yield
With CO2 In diethyl ether under N2; reacting ethene complex with CO2, 20°C, 1 atm, 30 min; filtering off ppt., 2nd crop from mother liquor by cooling to -20°C overnight; elem. anal.;	A 65% B n/a

1 ,6-dibromohexane (629-03-8) + trimethylphosphane (594-09-2) → (6-Bromhexyl)trimethylphosphoniumbromid (72385-53-6)

Conditions	Yield
In toluene for 72h; Ambient temperature;	100%

allyl bromide (106-95-6) + trimethylphosphane (594-09-2) → trimethyl-2-propen-1-ylphosphonium bromide (41301-43-3)

Conditions	Yield
In tetrahydrofuran; dichloromethane at 0 - 20℃; for 2.5h; Inert atmosphere;	100%
In diethyl ether Ambient temperature;
In toluene at 20℃; Inert atmosphere;
In dichloromethane for 12h; Inert atmosphere;

(bromomethyl)pentafluorobenzene (1765-40-8) + trimethylphosphane (594-09-2) → Trimethyl<(pentafluorphenyl)methyl>phosphoniumbromid (80431-31-8)

Conditions	Yield
In diethyl ether at 0℃; for 1h;	100%

1,10-diiododecane (16355-92-3) + trimethylphosphane (594-09-2) → (10-Iodo-decyl)-trimethyl-phosphonium; iodide (138730-46-8)

Conditions	Yield
In toluene for 72h; Ambient temperature;	100%

(2-chloroethyl)diphenylphosphane (5055-11-8) + trimethylphosphane (594-09-2) → (2-Diphenylphosphanyl-ethyl)-trimethyl-phosphonium; chloride (138710-61-9)

Conditions	Yield
In toluene for 72h; Heating;	100%

3-(diphenylphosphino)propyl chloride (57137-55-0) + trimethylphosphane (594-09-2) → (3-Diphenylphosphanyl-propyl)-trimethyl-phosphonium; chloride (170125-48-1)

Conditions	Yield
In toluene for 72h; Heating;	100%

Phosphoric acid (E)-2-chloro-1-chloromethyl-vinyl ester diethyl ester (89094-99-5) + trimethylphosphane (594-09-2) → O,O-diethyl α-(trimethylphosphoniummethyl)-β-chlorovinyl phosphate chloride (120115-73-3)

Conditions	Yield
at 0℃; for 2h;	100%
In diethyl ether for 12h; Ambient temperature; Yield given;

C16H31PSi + trimethylphosphane (594-09-2) → C19H40P2Si

Conditions	Yield
In pentane at 0℃; Addition;	100%

(η5-C5H5){P(OMe)3}2MoCPh + trimethylphosphane (594-09-2) → {(η5-C5H5)(PMe3)2(Cl)MoCPh}Cl

Conditions	Yield
In dichloromethane Irradiation (UV/VIS);	100%
In chloroform Irradiation (UV/VIS);	100%
In chloroform Irradiation (UV/VIS); addn. of PMe3 to the Mo compd. in CHCl3 and irradiation (Hanovia medium pressure mercury vapor lamp) for 30 min at room temp.; evapn. (vac.), dissolving in CH2Cl2 and pptn. with hexane; elem. anal.;	60%

Ir(C4(COOCH3)4)(C(CH2)3O){P(C6H5)3}2(CO)(1+)*BF4(1-)=Ir(C4(COOCH3)4)(C(CH2)3O){P(C6H5)3}2(CO)BF4 + trimethylphosphane (594-09-2) → Ir(C3H3O2)4{P(C6H5)3}2(CO)(CCHCH2CH2O)

Conditions	Yield
In acetone cooled to -76°C, stirred at 23°C for 3h; filtered; NMR, IR, elem. anal.;	100%

(bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum(0) (12146-37-1, 124717-04-0) + trimethylphosphane (594-09-2) → cis-bis(trimethylphosphine)tetracarbonylmolybdenum (16027-45-5) + bicyclo[2.2.1]hepta-2,5-diene (121-46-0)

Conditions	Yield
In tetrahydrofuran reaction in a calorimeter under argon;	A 100% B n/a

bis(cyclopentadienyl)titanium dichloride (1271-19-8) + trimethylphosphane (594-09-2) → bis(cyclopentadienyl)bis(trimethylphosphane)titanium(II)

Conditions	Yield
With Mg In tetrahydrofuran addn. of Mg (177 mmol) and P(CH3)3 (200 mmol) to soln. of ((C5H5)2TiCl2) (40.2 mmol) in THF under Ar; stirring for 20 h;; evapg. solvent at 1E-2 bar; extg. residue with pentane; crystn. at -78°C; elem. anal.;;	100%
With n-C4H9Li In tetrahydrofuran byproducts: LiCl, C4H8, C4H10; (Ar); to soln. of Ti complex was dropped hexane soln. of BuLi at -78°C within 0,5 h and stirred for 0,5 h, then was added PMe3, soln. was allowed to warm up to room temp. within 8 h and volatiles were removed at 0,1 Torr; pentane soln. of residue was filtered and filtrate cooled to -20°C, black crystals pptd., which were filtered off and dried at 0,01 Torr; elem. anal.;	90%
With Na#Hg In diethyl ether byproducts: NaCl; (Ar); a suspn. of Ti complex in a soln. of ligand added slowly to Na amalgam, stirred for 12 h; filtered, evapd. (Ar);	66%

cis-bis{(trimethylsilyl)methyl}(1,5-cyclooctadiene)platinum(II) (36223-69-5) + trimethylphosphane (594-09-2) → cis-bis(trimethylsilylmethyl)bis(trimethylphosphine)platinum(II)

Conditions	Yield
In toluene under Ar, heated to 60°C for 14 days; removal of solvent in vacuo, addn. of n-hexane, cooled to -25°C; elem. anal.;	100%

bis(ethenyldimethylsilylmethyl)(cod)Pt(II) + trimethylphosphane (594-09-2) → cis-bis(sila-neohexenyl)-bis-(trimethylphosphine)platinum(II)

Conditions	Yield
In benzene (under N2 or Ar) addn. of P-compd. to Pt-complex in benzene at room temp., standing overnight (ambient temp.); solvent removal (vac.); elem. anal.;	100%

{(Rh(η5-pentamethylcyclopentadienyl)Br2)2} + trimethylphosphane (594-09-2) → (η5-C5Me5)Rh{PMe3}Br2

Conditions	Yield
In dichloromethane PMe3 was condensed into a flask with complex and CH2Cl2 at -196°C, the mixt. was warmed to 25°C and stirred for 10 min;; recrystd. from CH2Cl2-hexane;;	100%

{(η4-2-methyl-1,3-pentadiene)cobalt(carbonyl)3} tetrafluoroborate (128205-88-9) + trimethylphosphane (594-09-2) → anti-{(η3-1-trimethylphosphonium-2-methyl-2-pentenyl)cobalt(carbonyl)3} tetrafluoroborate

Conditions	Yield
In nitromethane addn. of the Co complex to CH3NO2 at 0°C, stirring to complete dissoln., dropwise addn. of PMe3 in CH3NO2 and react. for 10-15 min; addn. of Et2O, removing the solvent using cannula and drying (vac.);	100%

(C5H5)MoCl2(P(C6H5)3)2 + trimethylphosphane (594-09-2) → cyclopentadienylmolybdenum(III)(PMe3)2Cl2

Conditions	Yield
In dichloromethane byproducts: P(C6H5)3; mixing of the Mo compd. with the free phosphine (molar ratio 2.6:1) in CH2Cl2;;	100%

C5H5V(CO)2(HCCH) + trimethylphosphane (594-09-2) → C5H5V(CO)(P(CH3)3)(HCCH)

Conditions	Yield
In pentane a solution of the alkyne-complex was cooled to -78°C; Me3P was added; standing over dry ice overnight; evaporation to dryness; dried in high vacuum;	100%

cyclopentadienylmolybdenum(III)(bis(diphenylphosphino)ethane)Cl2 + trimethylphosphane (594-09-2) → cyclopentadienylmolybdenum(III)(PMe3)2Cl2 + 1,2-bis-(diphenylphosphino)ethane (1663-45-2)

Conditions	Yield
In dichloromethane mixing of the Mo compd. with the free phosphine (molar ratio 2.3:1) in CH2Cl2;;	A 100% B n/a

C5H5V(CO)2(CH3CCCH3) + trimethylphosphane (594-09-2) → C5H5V(CO)(P(CH3)3)(CH3CCCH3)

Conditions	Yield
In pentane a solution of the alkyne-complex was cooled to -78°C; Me3P was added; standing over dry ice overnight; evaporation to dryness; dried in high vacuum;	100%

C5H5V(CO)2((CH3)3SiCCSi(CH3)3) + trimethylphosphane (594-09-2) → C5H5V(CO)(P(CH3)3)((CH3)3SiCCSi(CH3)3)

Conditions	Yield
In pentane a solution of the alkyne-complex was cooled to -78°C; Me3P was added; standing over dry ice overnight; evaporation to dryness; dried in high vacuum;	100%

C5H5V(CO)2(HCCC6H5) + trimethylphosphane (594-09-2) → C5H5V(CO)(P(CH3)3)(HCCC6H5)

Conditions	Yield
In pentane a solution of the alkyne-complex was cooled to -78°C; Me3P was added; standing over dry ice overnight; evaporation to dryness; dried in high vacuum;	100%

C5H5V(CO)2(C6H5CCC6H5) + trimethylphosphane (594-09-2) → C5H5V(CO)(P(CH3)3)(H5C6CCC6H5)

Conditions	Yield
In pentane a solution of the alkyne-complex was cooled to -78°C; Me3P was added; standing over dry ice overnight; evaporation to dryness; dried in high vacuum;	100%

(η5-C5H5)(CO)(NO)ReCH3 + trimethylphosphane (594-09-2) → Re(C5H5)(CO)(NO)(CH3)(P(CH3)3)2

Conditions	Yield
In hexane evapd.;	100%
In benzene-d6 under N2, soln. of educts in C6D6 heated at 51°C for 30 min; not isolated; detected by NMR;
In [(2)H6]acetone in NMR tube at room temp.;

3-(NNN'N'-tetramethylethylenediamine)-1,2-dicarba-3-palladadodecaborane (67538-15-2) + trimethylphosphane (594-09-2) → 3,3-bis(trimethylphosphine)-1,2-dicarba-3-palladadodecaborane (67538-14-1)

Conditions	Yield
In dichloromethane PMe3 passed into soln. of Pd complex in CH2Cl2; added hexane, filtered, washed with Et2O/acetone, dried in vac.; elem. anal.;	100%

(cyclopentadienyl)(carbonyl)(C8H6(C6H5))ruthenium + trimethylphosphane (594-09-2) → (cyclopentadienyl)(carbonyl)(C8H6(C6H5)(PMe3))ruthenium

Conditions	Yield
In benzene-d6 under N2; to Ru compd. in C6D6 addn. of PMe3 at room temp.; monitored by NMR; evapn. of solvent; elem. anal.;	100%

{Cp(PEt3)2molybdenum(III) dichloride} + trimethylphosphane (594-09-2) → cyclopentadienylmolybdenum(III)(PMe3)2Cl2 + triethylphosphine (554-70-1)

Conditions	Yield
In dichloromethane mixing of the Mo compd. with the free phosphine (molar ratio 4.5:1) in CH2Cl2;;	A 100% B n/a
In toluene mixing of the Mo compd. with the free phosphine (molar ratio 2.1:1) in toluene;;	A 100% B n/a

{Cp(PMePh2)2molybdenum(III) dichloride} + trimethylphosphane (594-09-2) → cyclopentadienylmolybdenum(III)(PMe3)2Cl2 + diphenyl(methyl)phosphine (1486-28-8)

Conditions	Yield
In toluene mixing of the Mo compd. with the free phosphine (molar ratio 2.1:1) in toluene;;	A 100% B n/a

{Cp(PMe2Ph)2molybdenum(III) dichloride} + trimethylphosphane (594-09-2) → cyclopentadienylmolybdenum(III)(PMe3)2Cl2 + Dimethyl(phenyl)phosphine (672-66-2)

Conditions	Yield
In toluene mixing of the Mo compd. with the free phosphine (molar ratio 2.2:1) in toluene;;	A 100% B n/a

t-butylaminotetraisopropoxy(phenylimido)tungsten(VI) + trimethylphosphane (594-09-2) → tetra-iso-propoxy(phenylimido)trimethylphosphinetungsten(VI) (97225-94-0)

Conditions	Yield
In petroleum ether PMe3 is added to soln. of W(NPh)(NH2CMe3)(OCHMe2)4 in petroleum ether and mixt. is stirred for 3 h; soln. is filtered, solvent removed;	100%

Upstream product

• 67-56-1 methanol 
• 75-15-0 carbon disulfide 
• 74-87-3 methylene chloride 
• 676-59-5 dimethylphosphane 
• 115-10-6 Dimethyl ether 
• 544-97-8 dimethyl zinc(II) 
• 1941-19-1 tetramethylphosphonium chloride 
• 60443-74-5 benzyltrimethyl phosphonium bromide 
• 7803-51-2 phosphan 
• 463-49-0 1,2-propanediene 
• 119405-80-0 C₃H₈P^(1-) 
• 676-83-5 methyldichlorophosphane 
• 917-54-4 methyllithium 
• 108-88-3 toluene 

Downstream Products

• 60443-74-5 benzyltrimethyl phosphonium bromide 
• 30417-67-5 benzyl-trimethyl-phosphonium; chloride 
• 58887-04-0 (2-hydroxyethyl)trimethylphosphonium chloride 
• 993-11-3 tetramethylphosphonium iodide 
• 75-46-7 trifluoromethan 
• 421-57-8 dimethyl(trifluoromethyl)phosphine 
• 75-50-3 trimethylamine 
• 676-96-0 Trimethylphosphine oxide 
• 30426-35-8 [Me₃PPPh₂][Cl] 
• 6063-72-5 trimethylsilyltrimethylphosphanimine 
• 41715-09-7 (Methoxy-phenyl-methyl)-trimethyl-phosphonium; chloride 
• 15107-02-5 Trimethylphosphinimid 
• 126580-25-4 Toluene-4-sulfonate(1-hydroxy-1-methyl-ethyl)-trimethyl-phosphonium; 
• 880343-42-0 chloro-tetramethyl-phosphorane 

Relevant articles and documents

Tetrakis(trimethylphosphine)nickel(0)

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

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).

Reactivity of (Pyridine-Diimine)Fe Alkyl Complexes with Carbon Dioxide

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