4099-46-1

Basic information

• Product Name: [BIS(TRIMETHYLSILYL)]SELENIDE
• Synonyms: [BIS(TRIMETHYLSILYL)]SELENIDE;Bis(trimethylsilyl)selenide,98%
• CAS NO: 4099-46-1
• Molecular Formula: C₆H₁₈SeSi₂
• Molecular Weight: 225.34
• Mol File: 4099-46-1.mol
• Article Data: 12

Chemical Properties

• Melting Point: -7°C
• Boiling Point: 58-9°C/11mmHg
• Flash Point: 59.6±18.7℃
• Appearance: /liquid
• Density: 0,9 g/cm3
• Vapor Pressure: 1.58mmHg at 25°C
• Refractive Index: 1.481
• Solubility: sol Et2O and THF.
• CAS DataBase Reference: [BIS(TRIMETHYLSILYL)]SELENIDE(CAS DataBase Reference)
• NIST Chemistry Reference: [BIS(TRIMETHYLSILYL)]SELENIDE(4099-46-1)
• EPA Substance Registry System: [BIS(TRIMETHYLSILYL)]SELENIDE(4099-46-1)

Safety Data

• TSCA: No
• Hazardous Substances Data: 4099-46-1(Hazardous Substances Data)

Usage

Chemical Properties

CLEAR COLOURLESS TO YELLOW LIQUID

Physical properties

bp 45–46°C/5.3 mmHg.

Uses

Bis(trimethylsilyl) Selenide can be used as synthesis of unsymmetrical selenides; generation of selenoaldehydes; reduction of sulfoxides, selenoxides, and telluroxides).Bis(trimethylsilyl) selenide reacts with equimolar amounts of n-butyllithium to generate Me3SiSeLi, alkylation of which then provides trimethylsilyl alkyl selenides. Similar treatment of Me3SiSeR with BuLi / R2X successfully leads to unsymmetrical selenides in good yields (eq 5).Use of acid chlorides in place of alkyl halides results in the formation of selenoesters.

Preparation

In the initial studies, bis(trimethylsilyl) selenide was synthesized by the following two methods: silylation of sodium selenide (or lithium selenide) with chlorotrimethylsilane (eq 1) or reaction of bromobenzene, magnesium, and selenium with chlorotrimethylsilane (eq 2).

InChI:InChI=1/C6H18SeSi2/c1-8(2,3)7-9(4,5)6/h1-6H3

Synthetic route

chloro-trimethyl-silane (75-77-4) → bis(trimethylsilyl)selenide (4099-46-1)

Conditions	Yield
With selenium; lithium triethylborohydride In tetrahydrofuran for 2h; Ambient temperature;	95%
With dilithium diselenide In tetrahydrofuran	80%
With lithium selenide; boron trifluoride diethyl etherate In tetrahydrofuran for 4h; Ambient temperature;	78%

trimethylsilyl bromide (2857-97-8) → bis(trimethylsilyl)selenide (4099-46-1)

Conditions	Yield
With seleno-aluminate for 3h; Ambient temperature;	62%

chloro-trimethyl-silane (75-77-4) + 2,4,6-trimethylphenyl bromide (576-83-0) → bis(trimethylsilyl)selenide (4099-46-1) + 2,4,6-Trimethylphenyl-trimethylsilyl-selenid

Conditions	Yield
Yield given. Multistep reaction;

chloro-trimethyl-silane (75-77-4) + phenylmagnesium bromide → phenyl trimethylsilyl selenide (33861-17-5) + bis(trimethylsilyl)selenide (4099-46-1)

Conditions	Yield
With selenium 1.) ether, r.t., 12 h; 2.) ether, r.t., 24 h; Yield given. Multistep reaction. Yields of byproduct given;

chloro-trimethyl-silane (75-77-4) → phenyl trimethylsilyl selenide (33861-17-5) + bis(trimethylsilyl)selenide (4099-46-1)

Conditions	Yield
With selenium; phenylmagnesium bromide 1.) ether, r.t., 12 h; 2.) ether, r.t., 24 h; Yield given. Multistep reaction. Yields of byproduct given;

tert-butylbis(trimethylsilyl)phosphine (42491-33-8) → bis(trimethylsilyl)selenide (4099-46-1) + t-butyl-perselenophosphonic anhydride (122631-90-7)

Conditions	Yield
With selenium

phenylmagnesium bromide → bis(trimethylsilyl)selenide (4099-46-1) + diphenylselenide (1132-39-4) + diphenyl diselenide (1666-13-3)

Conditions	Yield
With selenium; chloro-trimethyl-silane 1.) diethyl ether, 12 h, 2.) diethyl ether, 24 h; Yield given. Multistep reaction. Yields of byproduct given;

chloro-trimethyl-silane (75-77-4) + lithium n-butylselenolate (55163-69-4) → Di-n-butyl selenide (14835-66-6) + butyl(trimethylsilyl)selane (34044-18-3) + bis(trimethylsilyl)selenide (4099-46-1)

Conditions	Yield
In tetrahydrofuran; hexane at 20℃; Product distribution; Substitution;

bis(trimethylsilyl)selenide (4099-46-1) → 1,1,1,3,3,3-hexamethyl-disilazane (999-97-3) + Natrium-trimethylsilylselanolat

Conditions	Yield
With ammonia; sodium	A n/a B 100%
With ammonia; sodium

{WCl4(NCl)}2 + bis(trimethylsilyl)selenide (4099-46-1) → {CH3CN-WCl4(μ-dinitridoselenato)Cl4W-NCCH3}

Conditions	Yield
With acetonitrile In acetonitrile byproducts: (CH3)3SiCl; W-complex added to (Me3Si)2Se in CH3CN, refluxed for 4 h; solvent removed under vacuum; elem. anal., IR;	100%

tetrahydrofuran (109-99-9) + gallium(I) bromide + bis(trimethylsilyl)selenide (4099-46-1) → Ga24Se2Br18*12C4H8O

Conditions	Yield
In tetrahydrofuran; toluene byproducts: BrSiMe3; Se-compd. in THF added dropwise to GaBr in toluene/THF (3:1) at room temp., heated at reflux for 2 h; separated, concentrated in vac., kept at 50°C for a few days;	99%

bis(trimethylsilyl)selenide (4099-46-1) + diethylzinc (557-20-0) → zinc(II) selenide

Conditions	Yield
In 1,1,1-trichloroethane byproducts: Si(C2H5)(CH3)3; stirred at 75°C for 45 min; filtered, annealed (400°C, 18 h);	97%

tris-n-propylphosphine (2234-97-1) + bis(trimethylsilyl)selenide (4099-46-1) + copper (I) acetate (598-54-9, 142-71-2, 4180-12-5, 24381-58-6, 66760-61-0, 66760-62-1) → [Cu(P((CH2)2CH3)3)3SeSi(CH3)3] (265668-67-5)

Conditions	Yield
In diethyl ether; hexane byproducts: CH3CO2Si(CH3)3; 4 equiv of P(C3H7)3 were added to a soln. of CuO2CH3 in hexane-Et2O, cooled to -45°C, ((CH3)3Si)2Se was added, the mixt. was allowed to warm slowly with stirring to -15°C, stirredfor 2 h (N2); the mother liquor was removed, the crystals were dried under vac. at 0°C for 2 h, recrystd. from cold Et2O; elem. anal.;	97%
In diethyl ether CuOAc dissolved in ether with 4 equiv. propylphosphane, cooled to -40°C, 1 equiv Se(SiMe3)2 was added, warmed to -5°C with stirring for 3 h, solvent evapd.;	80%

bis(trimethylsilyl)selenide (4099-46-1) + diphenylselenoxide (7304-91-8) → Hexamethyldisiloxane (107-46-0) + diphenylselenide (1132-39-4)

Conditions	Yield
In tetrahydrofuran for 1h; Product distribution; Ambient temperature; var. selenium, tellurium and sulfur oxides, other solvents;	A n/a B 96%

bis(trimethylsilyl)selenide (4099-46-1) + silver(I) acetate (563-63-3) + ethyl-diphenyl-phosphane (607-01-2) → (diphenyl(ethyl)phosphine)3Ag(trimethylsilylselenolato) (935681-91-7)

Conditions	Yield
In diethyl ether byproducts: CH3C(O)OSi(CH3)3; (N2); Ag salt and P(C6H5)2C2H5 dissolved in Et2O, cooled to -70°C, Se(Si(CH3)3)2 added, stirred for ca 1 h; pptd. with cold hexane, sepd., washed (hexane), dried (vac.);	96%

bis(trimethylsilyl)selenide (4099-46-1) + copper (I) acetate (598-54-9, 142-71-2, 4180-12-5, 24381-58-6, 66760-61-0, 66760-62-1) + ethyl-diphenyl-phosphane (607-01-2) → (diphenyl(ethyl)phosphine)3Cu(trimethylsilylselenolato) (935681-85-9)

Conditions	Yield
In hexane; chloroform byproducts: CH3C(O)OSi(CH3)3; (N2); Cu salt dissolved with P(C6H5)2C2H5 in CHCl3 and hexane, cooled to-60°C, Se(Si(CH3)3)2 added, warmed slowly to -10°C; crystd. at -80°C for 4 d;	96%

bis(trimethylsilyl)selenide (4099-46-1) + 1,3-dimethylimidazolium tert-butylthiolate → 1,3-dimethylimidazolium trimethylsilylselenolate

Conditions	Yield
In tetrahydrofuran at 0 - 20℃; for 1h; Schlenk technique;	96%

bis(trimethylsilyl)selenide (4099-46-1) + phenyltin trichloride (1124-19-2) → C24H20Se6Sn4

Conditions	Yield
In toluene at 20℃; for 0.0833333h; Schlenk technique;	96%

bis(trimethylsilyl)selenide (4099-46-1) → trimethylsilyl iodide (16029-98-4)

Conditions	Yield
With iodine In m-xylene	94%

Cl2Sn{Co(CO)4}2 (15492-24-7) + bis(trimethylsilyl)selenide (4099-46-1) → ((CO)4Co)4Sn2Se2

Conditions	Yield
In tetrahydrofuran Ar or N2 atmosphere; addn. of Sn-org. compd. to soln. of Co-compd. in THF, stirring (12 h, room temp.); removal of volatiles, repeated washing (n-heptane), recrystn. (toluene/n-hexane); elem. anal.;	93%

N,N,N,N,-tetramethylethylenediamine (110-18-9) + bis(trimethylsilyl)selenide (4099-46-1) + zinc diacetate (557-34-6) → [(N,N'-tetramethylethylenediamine)Zn(SeSiMe3)2] (499106-44-4)

Conditions	Yield
In tetrahydrofuran under N2 atm. to soln. Zn(OAc)2 in THF TMEDA and Se(SiMe3)2 were added at 0°C and stirred for 15 min; THF was removed in vacuo, residue was washed with pentane and dried for 2 h at 0°C, crystn. from hexane-THF (3:1) at -80°C;	92%

bis(trimethylsilyl)selenide (4099-46-1) + dimethylcadmium (506-82-1) → cadmium(II) selenide

Conditions	Yield
In dichloromethane byproducts: Si(CH3)4; stirred at 25°C for 4 h; filtered, powder annealed in vacuo (400°C, 4 h); X-ray powder diffraction;	91%
In toluene byproducts: Si(CH3)4; stirred at 25°C, reaction is fairly slow, taked days to go compled; proton NMR;
In further solvent(s) under argon, soln. of Me2Cd in (n-C8H17)3P and soln. of ((CH3)3Si)2Se in (n-C8H17)3P are combined and added under vigorous stirring to (n-C8H17)3PO at 300°C, heat removed (180°C) then gradually raised to 230-260°C; cooled to 60°C, methanol added, centrifugated, dispersed (1-butanol), centrifugated, precipitate discarded, methanol added to the supernatant, flocculate rinsed (methanol), dried (vacuum);

tetrachloro(η-pentamethylcyclopentadienyl)tungsten(V) + bis(trimethylsilyl)selenide (4099-46-1) → anti-[(η(5)-pentamethyl-cyclopentadienyl)W(Se)(μ-Se)]2 + (η(5)-pentamethyl-cyclopentadienyl)W(Se)(μ-Se)Cl2

Conditions	Yield
In chloroform all manipulations under dry, O2-free Ar; soln. of compds. reacted at room temp. for 24 h; solvent evapd. in vac., separated by chromy., both compds. recrystd. from CHCl3/CHCl2/hexane at -78°C;	A 90.9% B 7.4%

[(AuCl)2(bis(diphenylphosphanyl)ethane)] + bis(trimethylsilyl)selenide (4099-46-1) → [Au18Se8(bis(diphenylphosphanyl)ethane)6]Cl2

Conditions	Yield
In dichloromethane byproducts: Me3SiCl, bis(diphenylphosphanyl)ethane; room temp.; stirred, 4 h; layered with n-heptane; crystd., 1 d; elem. anal.;	90%

[Fe(η-cyclopentadienyl)(CO)2(SnCl3)] + bis(trimethylsilyl)selenide (4099-46-1) → {C5H5(CO)2Fe}4Sn4Se6

Conditions	Yield
In tetrahydrofuran addn. of a soln. of (Me3Si)2Se in THF to a soln. of (Cp(CO)2Fe)SnCl3 in THF under Ar, color changes from deep brown to light red;; after 24 h evapn. (vac.), recrystn. from THF; elem. anal.;;	88.8%

(Me3Si)2C(Ph)C(Me3Si)NGaCl2 + bis(trimethylsilyl)selenide (4099-46-1) → [(Me3Si)2C(Ph)C(Me3Si)NGa(μ-Se)]2

Conditions	Yield
In toluene under N2 atm. (Me3Si)2Se was added at room temp. to soln. (Me3Si)2C(Ph)C(Me3Si)NGaCl2 in toluene and stirred for 2 h; solvent was removed in vacuo, residue was crystd. from toluene; elem. anal.;	88%

ethanol (64-17-5) + bis(trimethylsilyl)selenide (4099-46-1) + copper (I) acetate (598-54-9, 142-71-2, 4180-12-5, 24381-58-6, 66760-61-0, 66760-62-1) + diethyl-phenyl-phosphine (1605-53-4) → (diethyl(phenyl)phosphine)3CuSeH (935681-92-8)

Conditions	Yield
In diethyl ether (N2); Cu salt and P(C2H5)2C6H5 dissolved in Et2O, cooled to -60°C, Se(Si(CH3)3)2 added, stirred for 2 h with warming to ca -10°C; EtOH added, crystd. at -80°C for 12 h;	88%

bis(trimethylsilyl)selenide (4099-46-1) + C11H13Cl3O2Sn → C44H52O8Se6Sn4

Conditions	Yield
In toluene at 20℃; for 16h; Schlenk technique;	88%

bis(trimethylsilyl)selenide (4099-46-1) + Cu(1+)*C2H3O2(1-)*2C9H21P + [(Me2Ga)6Se(SeSiMe3)4] → [(iPr3PCu)4(MeGa)4Se6]

Conditions	Yield
With water In tetrahydrofuran at -35 - 20℃;	87%

tetrahydrofuran (109-99-9) + indium(III) chloride + n-butyllithium (109-72-8, 29786-93-4) + bis(trimethylsilyl)selenide (4099-46-1) → Li[In(SeSiMe3)4]*0.5THF

Conditions	Yield
Stage #1: tetrahydrofuran; n-butyllithium; bis(trimethylsilyl)selenide at 0 - 20℃; for 1.5h; Schlenk technique; Stage #2: indium(III) chloride In diethyl ether at -78 - 20℃; for 18h; Schlenk technique;	87%

3,5-Lutidine (591-22-0) + bis(trimethylsilyl)selenide (4099-46-1) + zinc diacetate (557-34-6) → [(3,5-lutidine)2zinc(SeSiMe3)2] (810667-24-4)

Conditions	Yield
In chloroform under N2 atm. Zn(OAc)2 was dissolved in CHCl3 and 3,5-lutidine, CHCl3 was removed in vacuo and replaced with THF after cooling to -78°C, Se(SiMe3)2 was added; soln. was concd. in vacuo at 0°C THF was removed in vacuo, cold pentane was added, ppt. was washed with pentane and dried in vacuo (0°C) for 30 min, recrystn. from CHCl3-pentane at -80°C for 2 days;	86%
In dichloromethane Se(SiMe3)2 added to soln. of Zn(CH3COO)2 solublized by 3,5-lutidine in CH2Cl2 at -78°C;

bis(trimethylsilyl)selenide (4099-46-1) + copper (I) acetate (598-54-9, 142-71-2, 4180-12-5, 24381-58-6, 66760-61-0, 66760-62-1) + diethyl-phenyl-phosphine (1605-53-4) → (diethyl(phenyl)phosphine)3Cu(trimethylsilylselenolato) (935681-84-8)

Conditions	Yield
In diethyl ether; hexane byproducts: CH3C(O)OSi(CH3)3; (N2); Cu salt dissolved in Et2O and hexane, P(C2H5)2C6H5 added, cooled to -60°C, Se(Si(CH3)3)2 added, warmed slowly to -10°C; crystd. at -80°C;	86%

bis(trimethylsilyl)selenide (4099-46-1) + P-(2,6-bis-(2,4,6-trimethylphenyl)phenyl)-P,P-dichlorophosphane (185522-84-3) → C48H50P2Se2 + C72H75P3Se3

Conditions	Yield
In tetrahydrofuran Inert atmosphere;	A 86% B 10%

bis(η5-cyclopentadienyldicarbonyliron)stannane dichloride + bis(trimethylsilyl)selenide (4099-46-1) → {(C5H5)(CO)2Fe}4Sn2Se2 + {C5H5(CO)2Fe}4Sn4Se6

Conditions	Yield
In tetrahydrofuran addn. of a soln. of (Me3Si)2Se in THF to a soln. of (Cp(CO)2Fe)2SnCl2 in THF under Ar, color changed from dark red to deep brown;; after 24 h evapn. (vac.), fractionated recrystn. from THF; elem. anal.;;	A 85% B 3%

Upstream product

• 42491-33-8 tert-butylbis(trimethylsilyl)phosphine 
• 75-77-4 chloro-trimethyl-silane 
• 55163-69-4 lithium n-butylselenolate 
• 2857-97-8 trimethylsilyl bromide 
• 576-83-0 2,4,6-trimethylphenyl bromide 

Downstream Products

• 107164-18-1 Benzyl-trimethylsilyl-selenid 
• 20601-83-6 mercury(II) selenide 
• 21931-14-6 (iodo)selenoborane 
• 16029-98-4 trimethylsilyl iodide 

Relevant articles and documents

Zinc Tin Chalcogenide Complexes and Their Evaluation as Molecular Precursors for Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe)

A series of five heteronuclear zinc tin chalcogenide complexes with the general formula [(tmeda)Zn(SnR2)2E3] (1-R, E = S; R = Me, Ph, tBu; 2-R, E = Se; R = Ph, tBu) have been synthesized and characterized by X-ray crystal structure analysis. In all cases, the six-membered ZnSn2E3 rings exhibit twist boat conformation. The presence of the molecular structures in solution is confirmed by 119Sn and 77Se NMR spectroscopy. Cothermolysis experiments using a mixture of complexes 1-R or 2-R and [(iPr3PCu)2(EC2H4E)]2 as a copper source were monitored by thermogravimetry and temperature dependent X-ray powder diffraction to examine the thermolysis reaction. According to Rietveld refinement, the solid residue consists of Cu2ZnSnS4 (up to 78 wt %) or Cu2ZnSnSe4 (up to 43 wt %) as the main product, respectively.

Synthesis and crystal structures of [(iPr3P)2Cu(μ- ESiMe3)(InMe3)] (E = S, Se): Lewis acid-base adducts with chalcogen atoms in planar coordination

The structures of [(iPr3P)2Cu(μ-SSiMe 3)(InMe3)] and [(iPr3P)2Cu(μ- SeSiMe3)(InMe3)] were determined by single-crystal X-ray diffraction. Both complexes are Lewis acid-base adducts of the InMe3 acceptor and the chalcogen donor atom linking a Me3Si group and a (iPr3P)2Cu moiety. They are very unstable under atmospheric conditions and decompose at ambient temperatures. Results of DFT calculations for these complexes and the related hypothetical [(Me 3P)2Cu(μ-SSiMe3)(InMe3)] compound show that the unusual planar coordination of the chalcogen atoms is due to steric crowding. Lewis acid-base adducts of trimethylindium and phosphane-stabilized copper(I) (trimethylsilyl)chalcogenolates were synthesized and characterized by X-ray crystal structure determination. They are very unstable under atmospheric conditions and decompose at ambient temperatures. DFT calculations reveal that the unusual planar coordination of the chalcogen atoms is due to steric crowding. Copyright

Synthesis and NMR investigation of selenobutyl substituted silanes and oligosilanes

The reaction of BuSeLi, made from BuLi and elemental selenium, with chlorosilanes MexPhySiCl4-x-y led to selenobutyl substituted derivatives. In the cases of polychlorosilanes formation of the completely substituted products MexPhySi(SeBu)4-x-y are favoured. Higher yields of partially substituted products could be obtained by reaction of chlorosilanes with BuSeH/NEt3. Besides monosilanes the reactions of several methylchlorodi-, tri- and isotetrasilanes with BuSeLi and BuSeH/NEt3 were also investigated. In SiClMe(SiClMe2)2 the chlorine substituent at the middle silicon atom is substituted by BuSeH/NEt3 at first selectively. All products were characterized by 1H, 13C, 29Si and 77Se NMR and trends of chemical shifts and coupling constants (1JSiSi, 1JSiSe, 2JSiSe) with the substitution pattern were investigated. Wiley-VCH Verlag GmbH, 2000.