15573-38-3

Usage

Uses

Used in Organic Synthesis:
TRIS(TRIMETHYLSILYL)PHOSPHINE is used as an intermediate for [organic synthesis] because of its reactivity with a range of electrophiles, allowing for the formation of substituted phosphines, phosphaalkenes, and phosphabenzenes.
Used as a Phosphorus Source:
TRIS(TRIMETHYLSILYL)PHOSPHINE is used as a user-friendly phosphorus source and alternative to [phosphine gas] due to its stability and reactivity, making it a safer and more convenient option for various applications.
Used in the Synthesis of (Me3Si)2PLi:
TRIS(TRIMETHYLSILYL)PHOSPHINE is used as a precursor for [(Me3Si)2PLi], a covalent synthon for the anion P3?, which is useful in the synthesis of various phosphorus-containing compounds.
Physical Properties:
TRIS(TRIMETHYLSILYL)PHOSPHINE has a melting point of 24 °C, a boiling point of 243-244 °C, a density of 0.863 g/cm3, and a refractive index ranging from 1.501 to 1.503.
Chemical Properties:
TRIS(TRIMETHYLSILYL)PHOSPHINE is a colorless to light yellow liquid that exhibits nucleophilic properties, allowing it to react with various electrophiles in organic synthesis.

Preparation

several preparative methods are known. These include the following: reaction of alkali metal phosphides (NaPH2, KPH2, Li3P, usually prepared by reaction of metal and phosphine gas or via metal alkyl derivative) with chlorotrimethylsilane or fluorotrimethylsilane in 1,2-dimethoxyethane or diethyl ether; reaction of sodium–potassium alloy with white or red phosphorus in refluxing 1,2- dimethoxyethane for 24 h followed by addition of chlorotrimethylsilane and heating at reflux for 72 h (good stirring is necessary for high yield of product), evaporation of the solvent, and vacuum distillation (75% yield); reaction of piperidinodichlorophosphine with lithium powder and chlorotrimethylsilane in refluxing tetrahydrofuran (71% yield); reaction of phosphine with excess of trimethylsilyl triflate in the presence of a tertiary amine in an inert solvent (Et2O) at low temperature (90% yield); reaction of phosphorus trichloride, magnesium, and chlorotrimethylsilane (62% yield). The last method is considered to be the most cost effective and also the safest approach.

InChI:InChI=1/C9H27PSi3/c1-11(2,3)10(12(4,5)6)13(7,8)9/h1-9H3

Synthetic route

trimethylsilyl trifluoromethanesulfonate (27607-77-8) → Tris(trimethylsilyl)phosphane (15573-38-3)

Conditions	Yield
With phosphan; triethylamine In dichloromethane at 8 - 20℃; for 1h; Solvent;	92%
With phosphan; triethylamine at 30 - 35℃; for 7h; Time; Inert atmosphere; Large scale;	90%
With phosphan; triethylamine In toluene at 30 - 35℃; for 7h; Inert atmosphere;

chloro-trimethyl-silane (75-77-4) → Tris(trimethylsilyl)phosphane (15573-38-3)

Conditions	Yield
With phosphorus; NaK alloy In 1,2-dimethoxyethane for 25h; Reflux;	78%
With 1-piperidinylphosphorous dichloride; lithium In tetrahydrofuran for 13h; Inert atmosphere; Reflux;	73%
With 1-piperidinylphosphorous dichloride; lithium In tetrahydrofuran Heating;	71%

chloro-trimethyl-silane (75-77-4) + P → Tris(trimethylsilyl)phosphane (15573-38-3)

Conditions	Yield
With potassium Sodium In 1,2-dimethoxyethane for 72h; Heating;	73%

trimethylsilyl iodide (16029-98-4) → Tris(trimethylsilyl)phosphane (15573-38-3)

Conditions	Yield
With phosphorous; Ti(N[t-Bu](3,5-Me2C6H3))3 In benzene at 20℃; Inert atmosphere;	86%

chloro-trimethyl-silane (75-77-4) + phosphorus → Tris(trimethylsilyl)phosphane (15573-38-3)

Conditions	Yield
Stage #1: phosphorus With sodium; potassium In 1,2-dimethoxyethane for 24h; Reflux; Inert atmosphere; Stage #2: chloro-trimethyl-silane at 30℃; Inert atmosphere;	82%

(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride (81476-73-5) + 2.5C4H8O*C15H37N2P2Si(1-)*Li(1+) → (iPr2N)2PP(SiMe3)H + bis(trimethylsilyl)phosphine (15573-39-4) + Tris(trimethylsilyl)phosphane (15573-38-3) + C39H76N4P6Zr (1432036-83-3) + tetrakis(diisopropylamino)diphosphane (128388-72-7) + 1,1-Bis-(diisopropylamino)-2,2-bis-(trimethylsilyl)-diphosphan (125484-53-9)

Conditions	Yield
In tetrahydrofuran at -70 - 20℃; for 25h;	A n/a B n/a C n/a D 0.020 g E n/a F n/a

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 15573-39-4 bis(trimethylsilyl)phosphine 
• 14177-93-6 trans-platinum(triethylphosphine)₂(chloro)₂ 
• 112438-35-4 (diisopropylamino){bis(trimethylsilyl)phosphino}boron chloride 
• 59610-41-2 lithium bis(trimethylsilyl)phosphanide-tetrahydrofuran (1/2) 
• 111960-37-3 bromocarbonylnitrosyl(pentamethylcyclopentadienyl)rhenium 
• 59624-91-8 LiP(Si(CH₃)3)2*2.8THF 
• 81476-73-5 (cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride 
• 27325-49-1 1-piperidinylphosphorous dichloride 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 16029-98-4 trimethylsilyl iodide 
• 109530-93-0 (B(Cl)N(C₂H₅)2CH)2 
• 109530-92-9 cis-1,2-bis(diisopropylaminochloroboryl)ethene 

Downstream Products

• 73260-79-4 (Bis-phenoxycarbonylmethyl-phosphanyl)-acetic acid phenyl ester 
• 73260-80-7 (Bis-p-tolyloxycarbonylmethyl-phosphanyl)-acetic acid p-tolyl ester 
• 190273-39-3 (1-Methylcyclohexyl-trimethylsiloxymethyliden)-trimethylsilylphosphin 
• 1450-14-2 1,1,1,2,2,2-hexamethyldisilane 
• 420-56-4 trimethylsilyl fluoride 
• 21658-00-4 Trimethylsilyl-bis-(trifluormethyl)-phosphin 
• 22398-80-7 indium(III) phosphide 
• 180397-99-3 [(C₆H₅)2ClAlP(Si(CH₃)3)3] 
• 1155266-28-6 C₃₇H₅₈O₂Si 
• 100938-86-1 2-(2,4,6-tri-tert-butylphenyl)phosphaacetylene 
• 1383813-43-1 [(C₆H₅CH₂)2InP(Si(CH₃)3)2]2 
• 1411976-35-6 C₁₂H₃₆PSi₄⁽¹⁺⁾*C₁₈H₄BF₁₂^(1-) 

Relevant academic research and scientific papers

Role of acid in precursor conversion during InP quantum dot synthesis

We have studied the speciation of P(SiMe3)3 during the synthesis of colloidal InP quantum dots in the presence of proton sources. Using 31P NMR spectroscopy, we show H3-nP(SiMe 3)n formation on exposure of P(SiMe3) 3 to a variety of protic reagents including water, methanol, and carboxylic acid, corroborating observations of P(SiMe3)3 speciation during the hot injection synthesis of InP QDs. Quantitative UV-vis comparisons between InP growth from P(SiMe3)3 and HP(SiMe3)2 show unambiguously that when total H +-content is accounted for, particle size, size dispersity, and concentration are indistinguishable for these two reagents. The dual role of myristic acid in P-Si bond cleavage and as a source of the myristate anion, an essential component of the quantum dot surface, is interrogated using tetrabutylammonium myristate, confirming that it is the protons that are responsible for increased quantum dot polydispersity. Together these data support the existence of a competing acid-catalyzed pathway in the conversion of P(SiMe3)3 to InP and demonstrate its impact. By preventing a constant solute supply and affecting the concentration of quantum dot surfactant over the course of the reaction, the existence of competing precursor conversion pathways is detrimental to formation of monodisperse colloids, explaining much of the irreproducibility in InP quantum dot syntheses to date.

A Simple Method for the Preparation of Tris(trimethylsilyl)phosphine

Tris(trimethylsilyl)phosphine is prepared in good yield by the reation of piperidinodichlorophosphine with lithium and chlorotrimethylsilane in boiling tetrahydrofuran.

Synthesis and X-ray crystal structure of novel tetramethylphosphonium dichlorodimethylaluminate

The reaction of tris(trimethylsilyl)phosphine with dimethylaluminum chloride in 1,2-dimethoxyethane (monoglyme) displays an important role as building blocks that results in the production of novel tetramethyl phosphonium dichlorodimethylaluminate and the already known dimer compound (bis(2,2-methoxy-ethanolato-O,O′)-tetramethyl-di-aluminum). The newly formed tetramethyl phosphonium dichlorodimethylaluminate [(CH3)4P]+[(CH3)2AlCl2]? crystallizes in the monoclinic space group P21/c, having unit cell with lattice constants a = 7.522, b = 11.644, c = 14.841 ?, and β = 99.32° includes four formula units. The mean values of the bond lengths are P-C 1.787 ?, Al-Cl 2.224 ?, and Al-C 1.966 ?. Both phosphorus and aluminum are tetrahedrally surrounded in organophosphonium-based cations and organoaluminium-based anions. The geometry of the dichlorodimethylaluminate anion shows a distorted tetrahedron.

1-Heteroakylation of tris(trimethylsilyl)phosphine

The 1-heteroalkylation of the tris-(trimethylsilyl)phosphine was thoroughly investigated using heterosubstituted methylamines, chloromethyl alkyl ethers, methyl chloroformate, paraformaldehyde, and dialkylformamides. Convenient methods for the synthesis of tris(dialkylaminomethyl)phosphines, tris(alkoxymethyl)phosphines, tris(methoxycarbonyl) phosphine, and several phosphaethylenes were proposed on the basis of the 1-heteroalkylation of tris(trimethylsilyl)phosphine as a valuable synthon.

A stable enol in small ring systems: Clear differentiation between penta- and tri-valency of phosphorus atoms

The first stable enols in 1,2-dihydrophosphetes 6 and 10 were synthesized and structurally characterized with intermolecular hydrogen bonds to phosphoryl groups in 10-membered dimeric structures; in contrast, trivalent analogue 9 exists in keto-form, where such stabilization by hydrogen bonds is not feasible. The Royal Society of Chemistry.

Simple conversion of trisodium phosphide, Na3P, into silyl- and cyanophosphides and the structure of a terminal silver phosphide

A reaction of trisodium phosphide (Na3P) with chlorosilanes allows for simple derivatization into silyl- and cyano-substituted phosphanide species which were compared with each other. The recently discovered cyano(triphenylsilyl)phosphanide shows unique coordination properties compared to bis(silyl)phosphides.

Method for producing InP quantum dot precursors and method for producing InP quantum dots

The present invention pertains to a method for producing InP quantum dot precursors from a phosphorus source and an indium source, wherein a silylphosphine compound represented by general formula (1), which contains a compound represented by general formula (2) in an amount of 0.3 mol% or less, is used as the phosphorus source. Further, the present invention provides a method for producing InP quantum dots, said method comprising heating the InP quantum dot precursors at a temperature of 200-350 DEG C inclusive to thereby give InP quantum dots. (R is as defined in the description.).

Exploration of Novel α,ω-Substituted Diphosphatrisilanes by Combining Experimental Methods and DFT Calculations

The novel diphosphatrisilanes {(R2P-Si(SiMe3)2-)2-SiMe2} [R = Ph, H] and the cyclophosphatrisilabutanes {R–PSi3} [R = H, SiMe3] have been prepared via salt metathesis reactions between phosphanides and 2,4-dihalogenated pentasilanes and characterized via NMR spectroscopy. The experimental results were supported by DFT calculations. Although P–Si bond formation was observed in all cases, the outcome of the reactions varied depending on the nature of ligands on the phosphanides, forming either linear diphosphatrisilanes or cyclic phosphatrisilacyclobutanes. DFT studies were performed to get a better understanding of the reactions. The precursor silanes were fully characterized using NMR spectroscopy and single-crystal X-ray diffraction and offer interesting building blocks. In addition, a modified route for the synthesis of P(TMS)3 was successfully carried out, achieving high yields of up to 73 %, circumventing the use of white phosphorus and phosphine gas during the reaction.

PROCESS FOR PRODUCING SILYL PHOSPHINE COMPOUND AND SILYL PHOSPHINE COMPOUND

The process for producing a silyl phosphine compound of the present invention comprises a first step of mixing a solvent having a relative dielectric constant of not more than 4, a basic compound, a silylating agent and phosphine to obtain a solution containing a silyl phosphine compound, a second step of removing the solvent from the solution containing a silyl phosphine compound to obtain a concentrated solution of a silyl phosphine compound, and a third step of distilling the concentrated solution of a silyl phosphine compound to obtain the silyl phosphine compound. The silyl phosphine compound of the present invention is a silyl phosphine compound represented by the following general formula (1), wherein a content of a compound represented by the following general formula (2) is not more than 0.5 mol %. (For explanatory notes of the formulas, see the specification.)

Synthetic studies on a series of functionalized pyrylium salts, 4-chloro- and 4-bromophosphinines

A series of new pyrylium salts that bear sulfonate and phosphonate groups were obtained from the reactions between 2,6-diphenyl-4H-pyran-4-one, sulfonic anhydride, and chlorophosphates, and analyzed spectroscopically. Furthermore, treatment of 2,6-diphenyl-4H-pyran-4-one with phosphoryl chloride or bromide afforded the corresponding 4-chloro- and 4-bromopyrylium tetrafluoroborates in good yield. Subsequently, the synthesis of the corresponding 4-chloro- and 4-bromophosphinines was accomplished by treating the respective chloro- and bromopyrylium tetrafluoroborates with tris(trimethylsilyl)phosphine.