594-09-2

Usage

Chemical Description

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

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].

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 
• 115-10-6 Dimethyl ether 
• 544-97-8 dimethyl zinc(II) 
• 1941-19-1 tetramethylphosphonium chloride 
• 60443-74-5 benzyltrimethyl phosphonium bromide 
• 74-87-3 methylene chloride 
• 7803-51-2 phosphan 
• 64-17-5 ethanol 
• 119405-80-0 C₃H₈P^(1-) 
• 463-49-0 1,2-propanediene 
• 676-83-5 methyldichlorophosphane 
• 108-88-3 toluene 
• 101-02-0 triphenyl phosphite 
• 917-64-6 methyl magnesium iodide 

Downstream Products

• 60443-74-5 benzyltrimethyl phosphonium bromide 
• 30417-67-5 benzyl-trimethyl-phosphonium; chloride 
• 58887-04-0 (2-hydroxyethyl)trimethylphosphonium chloride 
• 30426-35-8 [Me₃PPPh₂][Cl] 
• 126580-27-6 Trimethyl-(phenyl-trimethylsilanyloxy-methyl)-phosphonium; chloride 
• 126580-25-4 Toluene-4-sulfonate(1-hydroxy-1-methyl-ethyl)-trimethyl-phosphonium; 
• 80431-31-8 Trimethyl<(pentafluorphenyl)methyl>phosphoniumbromid 
• 676-96-0 Trimethylphosphine oxide 
• 880343-42-0 chloro-tetramethyl-phosphorane 
• 58201-66-4 (bromodifluormethyl)triphenylphosphonium bromide 
• 106-98-9 1-butylene 
• 187737-37-7 propene 
• 34557-54-5 methane 
• 31386-70-6 C₂H₆P^(1-) 

Relevant academic research and scientific papers

Formation and reactivity of the ethylene complex Cp2TiC2H4. The crystal structure of (Cp2TiEt)2O

The reaction of Cp2Ti(PMe3)2 (1) and ethylene affords the 16-electron species Cp2TiC2H4 (2).In a reaction of 2 and ethylene under pressure, 1-butene and trans-2-butene are formed catalytically.With water, 2 reacts to give the dinuclear μ-oxo complex (Cp2TiEt)2O (3) the structure of which has been determined by X-ray diffraction.

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.

Benzenedithiolate-bridged MoFe complexes: Structures, oxidation states, and reactivities

Two benzendithiolate-bridged MoFe complexes, [(Me3P)2(CO)2Mo(μ-S2C6H4)Fe(CO)3] (1) and [(Me3P)(CO)3Mo(μ-S2C6H4)Fe(CO)3] (2), were synthesized by reacting [Mo(S2C6H4)(CO)2(PMe3)2] (3) with Fe(CO)5. Each complex has a direct Mo-Fe bond that is supported by a bridging benzenedithiolate ligand and a semi-bridging carbonyl ligand as elucidated by single-crystal X-ray diffractometry. The structural data and differences in reactivity of these complexes suggest that monophosphine complex 2 is formed via diphosphine complex 1. The reaction of 2 with PMe3 gives the diiron bis(dithiolate) complex, [Fe(S2C6H4)(CO)2(PMe3)]2 (4), rather than 1. 57Fe M?ssbauer and X-ray photoelectron spectroscopy studies reveal the oxidation states of the metal centers in 2 to be Fe0 and MoII. This journal is

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).

Experimental and Computational Evaluation of Tantalocene Hydrides for C-H Activation of Arenes

Half a century ago, tantalocene hydrides (especially Cp2TaH3, where Cp = η5-C5H5) were reported to catalyze H/D exchange with arenes. However, there has been very little follow-up to the seminal reports, and numerous questions about this chemistry remain unanswered. In an effort to better evaluate the potential of tantalocene hydrides for processes involving C-H activation, we have conducted a series of experimental and computational studies on these complexes. Density functional theory (DFT) calculations support a mechanism for arene C-H activation involving oxidative addition at transient TaIII, rather than a σ-bond metathesis mechanism at TaV. Comparisons were made between thermal and photochemical conditions for the reaction of Cp2TaH3 with benzene-d6, and H/D exchange was found to be moderately faster under thermal conditions. In a reaction with toluene, Cp2TaH3 activates the aromatic C(sp2)-H bonds but not the benzylic bonds. DFT calculations suggest that benzylic C-H activation at TaIII has a barrier similar to aromatic C-H activation, but that formation of a I -complex with Cp2TaH directs preferential aromatic C-H activation. Analogous complexes containing the less labile permethylated ligand Cp? (Cp? = η5-C5Me5) were also evaluated for their ability to catalyze H/D exchange with benzene-d6, but these complexes are less active than Cp2TaH3. DFT calculations indicate that the methyl groups of Cp? disfavor I -coordination of an arene to the TaIII intermediate.

Six-Coordinate Ferrous Nitrosyl Complex FeII(TTP)(PMe3)(NO) (TTP = meso-Tetra-p-tolylporphyrinato Dianion)

Low-temperature in situ Fourier transform infrared and UV-vis measurements show that trimethylphosphine (PMe3) reacts with microporous layers of FeII(TTP)(NO) (TTP = meso-tetra-p-tolylporphyrinato dianion; NO = nitric oxide) to form

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

A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics

The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.

Bond formation and coupling between germyl and bridging germylene ligands in dinuclear palladium(I) complexes

The dinuclear palladium(I) complexes [L-(Ar2HGe)Pd(μ-GeAr2)2Pd(GeHAr2)L] (Ar = Ph, p-Tol; L= PMe3, tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge...Ge bond lengths of 2.8263(4) ? (L = PMe3) and 2.928(1) ? (L = tBuNC), which are close to the longest Ge-Ge bond reported to date [2.714(1) ?]. Significant Ge...Ge interactions between the germylene and germyl ligands (PMe3 complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe3 ligands increases the Ge...Ge interaction, and simultaneously activates two Pd-Ge bonds. Adding the chelating diphosphine 1,2-bis(diethylphosphino)-ethane (depe) to the PMe3 complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.

A fast catalytic process of transfer of a phosphorus atom: How folding of the reagent is related to its catalytic activity. a possible correlation with rna behavior

A simple and very fast process of transfer of a phosphorus atom, performed by a simple molecule acting as catalyst in an almost infinite catalytic cycle is described. The catalyst donates a P atom to a mixture of two different Grignard reagents giving, in a very fast and in a highly selective manner, only one phosphorus-containing compound with an enormous rate enhancement with respect to the corresponding no-catalyzed reaction which gives a final cluttered mixture of many organophosphorus products. The focal factor to explain this highly selective process of P transport lies in the folded structure of the reagent with particular angles around the phosphorus atom which can facilitate the formation of cyclic trigonal bipyramidal pentacoordinated species and then its catalytic activity. In a similar manner, RNA can adopt, in a precise position, a particular three-dimensional structure that might facilitate the formation of pentacoordinated species leading to the catalytic function.