WO2022087036A1 - Method for preparing iodosilanes - Google Patents

Method for preparing iodosilanes Download PDF

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Publication number
WO2022087036A1
WO2022087036A1 PCT/US2021/055707 US2021055707W WO2022087036A1 WO 2022087036 A1 WO2022087036 A1 WO 2022087036A1 US 2021055707 W US2021055707 W US 2021055707W WO 2022087036 A1 WO2022087036 A1 WO 2022087036A1
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formula
compound
phenyl
alkyl
substituted
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French (fr)
Inventor
Scott A. Laneman
Jonathan W. DUBE
James M. STUBBS
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Entegris Inc
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Entegris Inc
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Priority to KR1020267002623A priority Critical patent/KR20260025875A/en
Priority to EP21883749.0A priority patent/EP4232410A4/en
Priority to KR1020237016859A priority patent/KR20230088488A/en
Priority to JP2023524893A priority patent/JP7604641B2/en
Priority to CN202180079218.9A priority patent/CN116457310A/en
Priority to CA3199231A priority patent/CA3199231A1/en
Publication of WO2022087036A1 publication Critical patent/WO2022087036A1/en
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Priority to JP2024157269A priority patent/JP2025003979A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/025—Silicon compounds without C-silicon linkages

Definitions

  • This invention belongs to the field of silicon chemistry. In particular, it relates to methodology for preparing di- and tri-iodosilanes.
  • Halosilanes are useful as precursors in the manufacturing of microelectronic devices; in particular, halosilanes such as H2Sil2 and HSiL are useful as precursor compounds for the deposition of silicon-containing films used in the manufacture of microelectronic devices.
  • Current solution based synthetic methodology describes the synthesis of H2Sil2 and other select iodosilanes from (i) aryl silanes (Keinan et al. J. Org. Chem., Vol. 52, No. 22, 1987, pp. 4846-4851; Kerrigan et. al. U.S. Patent No. 10,106,425 or (ii) halosilanes such as (U.S. Patent No. 10,384,944).
  • Keinan et al. describe a synthetic method towards SiH2l2 formation that employs stoichiometric treatment of an arylsilane, with iodine in the presence of a catalyst such as ethyl acetate.
  • the reaction by-products are the aromatic function from the arylsilane, liberated as benzene, and a complicated by-product mixture resulting from ethyl acetate decomposition. Tedious separation of the reaction by-products from the desired SiH2l2 complicates the process.
  • arylsilane-based methods for preparing halosilanes typically generate product contaminated with idodine and/or hydrogen iodide, which are deleterious to the desired iodosilane product, so often antimony, silver, or copper are utilized to stabilize the iodosilane product.
  • U.S. Patent No. 10,106,425 teaches the use of an arylsilane, as reactant.
  • the process as disclosed generates toluene as a by-product and is thus claimed as a less hazardous alternative to the Keinan method which generates benzene from Phenyl- SiH 3 .
  • U.S. Patent No. 10,384,944 describes a halide exchange between, for example, Lil and thereby generating LiCl and in a halogen exchange reaction.
  • the invention provides methodology for preparing highly desired iodosilanes such as via treatment of certain dialkylamido- silanes with an acyl iodide.
  • diiodosilane can be prepared from the reaction of bis(diethylamino)silane with benzoyl iodide, The reaction surprisingly results in the substitution of the alkylamino group on the aminosilane with an iodo group. This transformation readily occurs at room temperature and atmospheric pressure and can be conducted neat as well as in the presence of aprotic solvents.
  • the disclosure provides a method for preparing a compound having the formula(I): wherein x is 1 or 2, y is 2 or 3, and the sum of x plus y is 4, the method comprising: contacting a compound of the formula (A): wherein (i) each R 1 and each R 2 is independently chosen from a alkyl group, a cycloaliphatic group, or hydrogen, or (ii) R 1 and R 2 are taken together with the nitrogen atom to which they are bonded to form a nitrogen-containing saturated or aromatic ring, provided that no more than one of R 1 and R 2 is hydrogen; with a compound of the formula: wherein R 3 is chosen from alkyl, substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (I).
  • the disclosure provides a method for preparing a compound having the formula (II): wherein y is 2 or 3, z is 0 or 1, and the sum of y and z is 3, the method comprising: contacting a compound of the formula (B): wherein (i) each R 1 and each R 2 is independently chosen from a C 1 - C 6 alkyl group, a cycloaliphatic group, or hydrogen, or (ii) R 1 and R 2 are taken together with the nitrogen atom to which they are bonded to form a C4-C7 nitrogen-containing saturated or aromatic ring, provided that no more than one of R 1 and R 2 is hydrogen; with a compound of the formula: wherein R 3 is chosen from C 1 -C 6 alkyl, C 1 -C 6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (II)
  • the product of formula (I) is produced when the reactant of formula (A) is utilized and the product of formula (II) is produced when the reactant of formula (B) is utilized.
  • the compound of formula (I) is H 2 SiI 2 .
  • the compound of formula (I) is HSiI 3 .
  • substituted phenyl denotes a phenyl group substituted one to five times with a group chosen from C 1 -C 6 alkyl, C 1 -C 6 alkylamino, di-(C 1 -C 6 alkyl)amino, and halo. In one embodiment, halo is fluoro.
  • substituted C 1 -C 6 alkyl denotes a C 1 -C 6 alkyl group substituted one to five times with a group chosen from C 1 -C 6 alkylamino, di-(Ci-C6 alkyl)amino, and halo.
  • substituted benzyl denotes a benzyl group having one to five substituents on the aromatic ring chosen from C 1 -C 6 alkylamino, di-(C 1 -C 6 alkyl)amino, and halo.
  • the methodology of the invention can be practiced neat or in the presence of an aprotic solvent which is non-reactive with the starting materials or iodosilane products.
  • solvents include aliphatic, aromatic, and halogenated hydrocarbon solvents which are devoid of moieties and functional groups such as oxygen, esters, carboxy groups, and ketones. Examples include benzene, toluene, hexane, cyclohexane, pentane, dichloromethane, 1,2-dichloroethane, tetralin, decalin, mesitylene, dibromoethane, tetrachloroethylene, or chlorobenzene, and the like.
  • the reaction generally proceeds at room temperature and atmospheric pressure.
  • the method for preparing the precursor compounds of the invention can be conducted in standard batch or continuous mode reactors.
  • One of ordinary skill in the art would recognize the scale and type of reactors which could be utilized in the context of the reagents and products so produced.
  • Compounds of the formulae (I) and (II) are useful as precursors in the formation of silicon-containing films on the surface of a microelectronic device by methods such as atomic layer deposition (see for example, U.S. Patent Nos. 10,580,645 and 10,424,477, incorporated herein by reference). Also, by way of example, compounds of formulae (I) and (II) can be introduced into a deposition chamber for the purposes of thermal CVD or ALD, or for the purposes of performing plasma-enhanced ALD or CVD.
  • a co-reactant gas can be introduced to deposit an SiO 2 film, via oxidation in an oxidizing environment with O 2 , O 3 , N 2 O, or mixtures thereof.
  • compounds of formulae (I) and (II) can be introduced into a deposition chamber for the purposes of thermal CVD or ALD, or for the purposes of performing plasma-enhanced ALD or CVD.
  • a co-reactant gas can be introduced to deposit a silicon nitride film, via nitridation with N2, NH3, hydrazine or alkylhydrazine containing mixtures. The deposited films serve as dielectric layers within the microelectronic device. Examples
  • the disclosure provides a method for preparing a compound having the formula (I): wherein x is 1 or 2, y is 2 or 3, and the sum of x plus y is 4, the method comprising: contacting a compound of the formula (A): wherein (i) each R 1 and each R 2 is independently chosen from a C 1 -C 6 alkyl group, a C 3 -C 8 cycloaliphatic group, or hydrogen, or (ii) R 1 and R 2 are taken together with the nitrogen atom to which they are bonded to form a C4-C7 nitrogen-containing saturated or aromatic ring, provided that no more than one of R 1 and R 2 is hydrogen; with a compound of the formula: wherein R 3 is chosen from C 1 -C 6 alkyl, C 1 -C 6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of
  • the disclosure provides the method of the first aspect, wherein the compound of formula (I) is
  • the disclosure provides the method of the first aspect, wherein the compound of formula (I) is HSiR.
  • the disclosure provides the method of the first or second aspect, wherein R 1 and R 2 are chosen from methyl, ethyl, propyl, sec-butyl, and t-butyl.
  • the disclosure provides the method of any one of the first through fourth aspects, wherein at least one of R 1 and R 2 is t-butyl.
  • the disclosure provides the method of the first, second, or third aspects, wherein at least one of R 1 and R 2 is cyclohexyl.
  • the disclosure provides the method of the first, second, or third aspects, wherein R 1 and R 2 are taken together with the nitrogen atom to which they are attached, to form a pyrrole, pyrrolidine, or piperidine ring.
  • the disclosure provides the method of any one of the first through the seventh aspects, wherein R 3 is C 1 -C 6 alkyl.
  • the disclosure provides the method of any one of the first through seventh aspects, wherein R 3 is phenyl.
  • the disclosure provides the method of any one of the first through seventh aspects, wherein R 3 is substituted phenyl.
  • the disclosure provides the method of any one of the first through seventh, or tenth aspects, wherein R 3 is 4-fluorophenyl.
  • the disclosure provides the method of any one of the first through seventh or tenth aspects, wherein R 3 is 3,5-difluorophenyl.
  • the disclosure provides the method of the first, second, or third aspects, wherein at least one of R 1 and R 2 is ethyl and R 3 is methyl or phenyl.
  • the disclosure provides a method for preparing a compound having the formula (II):
  • each R 1 and each R 2 is independently chosen from a C 1 -
  • R 1 and R 2 are taken together with the nitrogen atom to which they are bonded to form a C 4 -C 7 nitrogen-containing saturated or aromatic ring, provided that no more than one of R 1 and R 2 is hydrogen; with a compound of the formula: wherein R 3 is chosen from C 1 -C 6 alkyl, C 1 -C 6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (II).
  • the disclosure provides the method of the fourteenth aspect, wherein R 1 and R 2 are chosen from methyl, ethyl, propyl, sec-butyl, and t-butyl.
  • the disclosure provides the method of the fourteenth aspect, wherein at least one of R 1 or R 2 is t-butyl.
  • the disclosure provides the method of the fourteenth aspect, wherein at least one of R 1 or R 2 is cyclohexyl.
  • the disclosure provides the method of the fourteenth aspect, wherein R 1 and R 2 are taken together with the nitrogen atom to which they are attached, to form a pyrrole, pyrrolidine, or piperidine ring.
  • the disclosure provides the method of any one of the fourteenth through eighteenth aspects, wherein R 3 is C 1 -C 6 alkyl.
  • the disclosure provides the method of any one of the fourteenth through eighteenth aspects, wherein R 3 is phenyl.
  • the disclosure provides the method of the fourteenth aspect, wherein at least one of R 1 and R 2 is ethyl and R 3 is methyl or phenyl.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

Provided is methodology for the preparation of highly-desired iodosilanes such as H2SiI2 and HSiI3, via a reaction of alkylaminosilanes with certain substituted acid iodides. In one embodiment, bis(diethylamino)silane is reacted with benzoyl iodide to provide diiodosilane.

Description

METHOD FOR PREPARING IODOSILANES
Technical Field
[0001] This invention belongs to the field of silicon chemistry. In particular, it relates to methodology for preparing di- and tri-iodosilanes.
Background
[0002] Halosilanes are useful as precursors in the manufacturing of microelectronic devices; in particular, halosilanes such as H2Sil2 and HSiL are useful as precursor compounds for the deposition of silicon-containing films used in the manufacture of microelectronic devices. Current solution based synthetic methodology describes the synthesis of H2Sil2 and other select iodosilanes from (i) aryl silanes (Keinan et al. J. Org. Chem., Vol. 52, No. 22, 1987, pp. 4846-4851; Kerrigan et. al. U.S. Patent No. 10,106,425 or (ii) halosilanes such as (U.S. Patent No. 10,384,944).
Figure imgf000002_0001
[0003] Keinan et al. describe a synthetic method towards SiH2l2 formation that employs stoichiometric treatment of an arylsilane, with iodine in the presence of a
Figure imgf000002_0002
catalyst such as ethyl acetate. The reaction by-products are the aromatic function from the arylsilane, liberated as benzene, and a complicated by-product mixture resulting from ethyl acetate decomposition. Tedious separation of the reaction by-products from the desired SiH2l2 complicates the process. In addition, arylsilane-based methods for preparing halosilanes typically generate product contaminated with idodine and/or hydrogen iodide, which are deleterious to the desired iodosilane product, so often antimony, silver, or copper are utilized to stabilize the iodosilane product.
[0004] U.S. Patent No. 10,106,425 teaches the use of an arylsilane, as
Figure imgf000002_0003
reactant. The process as disclosed generates toluene as a by-product and is thus claimed as a less hazardous alternative to the Keinan method which generates benzene from Phenyl- SiH3. U.S. Patent No. 10,384,944 describes a halide exchange between, for example, Lil and
Figure imgf000002_0004
thereby generating LiCl and
Figure imgf000002_0005
in a halogen exchange reaction.
Summary [0005] In summary, the invention provides methodology for preparing highly desired iodosilanes such as via treatment of certain dialkylamido- silanes with an
Figure imgf000003_0005
acyl iodide. In one example, diiodosilane can be prepared from the reaction of bis(diethylamino)silane with benzoyl iodide, The reaction surprisingly results in the substitution of the alkylamino group on the aminosilane with an iodo group. This transformation readily occurs at room temperature and atmospheric pressure and can be conducted neat as well as in the presence of aprotic solvents.
Detailed Description
[0006] As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
[0007] The term “about” generally refers to a range of numbers that is considered equivalent to the recited value (e.g., having the same function or result). In many instances, the term “about” may include numbers that are rounded to the nearest significant figure.
[0008] Numerical ranges expressed using endpoints include all numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4 and 5).
[0009] In a first aspect, the disclosure provides a method for preparing a compound having the formula(I):
Figure imgf000003_0001
wherein x is 1 or 2, y is 2 or 3, and the sum of x plus y is 4, the method comprising: contacting a compound of the formula (A):
Figure imgf000003_0002
wherein (i) each R1 and each R2 is independently chosen from a alkyl
Figure imgf000003_0003
group, a
Figure imgf000003_0004
cycloaliphatic group, or hydrogen, or (ii) R1 and R2 are taken together with the nitrogen atom to which they are bonded to form a nitrogen-containing saturated or aromatic ring, provided that no more than one of R1 and R2 is hydrogen; with a compound of the formula:
Figure imgf000004_0001
wherein R3 is chosen from alkyl, substituted alkyl, benzyl,
Figure imgf000004_0002
Figure imgf000004_0003
substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (I).
[0010] In a second aspect, the disclosure provides a method for preparing a compound having the formula (II):
Figure imgf000004_0004
wherein y is 2 or 3, z is 0 or 1, and the sum of y and z is 3, the method comprising: contacting a compound of the formula (B):
Figure imgf000004_0005
wherein (i) each R1 and each R2 is independently chosen from a C1- C6 alkyl group, a cycloaliphatic group, or hydrogen, or (ii) R1 and R2 are taken together with the nitrogen atom to which they are bonded to form a C4-C7 nitrogen-containing saturated or aromatic ring, provided that no more than one of R1 and R2 is hydrogen; with a compound of the formula:
Figure imgf000005_0001
wherein R3 is chosen from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (II).
[0011] In the above process, it will be appreciated that the product of formula (I) is produced when the reactant of formula (A) is utilized and the product of formula (II) is produced when the reactant of formula (B) is utilized. In one embodiment, the compound of formula (I) is H2SiI2. In another embodiment, the compound of formula (I) is HSiI3.
[0012] In one embodiment, the compound of the formula
(H)xSi(N(R1)( R2))y (A), is chosen from compounds such as
H2Si(N(CH3)2)2;
H2Si(N(CH2CH3)2)2;
H2Si(N(CH2CH3)(CH3))2
H2Si(N(CH2CH2CH3)2)2;
H2Si(N(CH2CH2CH2CH3)2)2;
H2Si(N(t-butyl)2)2;
H2Si(N(H)(t-butyl))2;
HSi(N(CH3)2)3;
HSi(N(CH2CH3)2)3;
HSi(N(CH2CH2CH3)2)3;
HSi(N(CH2CH2CH2CH3)2)3;
HSi(N(t-butyl)2)3; and the like.
[0013] As used herein, the term “substituted phenyl” denotes a phenyl group substituted one to five times with a group chosen from C1-C6 alkyl, C1-C6 alkylamino, di-(C1-C6 alkyl)amino, and halo. In one embodiment, halo is fluoro. [0014] As used herein, the term “substituted C1-C6 alkyl” denotes a C1-C6 alkyl group substituted one to five times with a group chosen from C1-C6 alkylamino, di-(Ci-C6 alkyl)amino, and halo.
[0015] As used herein, the term “substituted benzyl” denotes a benzyl group having one to five substituents on the aromatic ring chosen from C1-C6 alkylamino, di-(C1-C6 alkyl)amino, and halo.
[0016] The methodology of the invention can be practiced neat or in the presence of an aprotic solvent which is non-reactive with the starting materials or iodosilane products. Such solvents include aliphatic, aromatic, and halogenated hydrocarbon solvents which are devoid of moieties and functional groups such as oxygen, esters, carboxy groups, and ketones. Examples include benzene, toluene, hexane, cyclohexane, pentane, dichloromethane, 1,2-dichloroethane, tetralin, decalin, mesitylene, dibromoethane, tetrachloroethylene, or chlorobenzene, and the like.
[0017] The reaction generally proceeds at room temperature and atmospheric pressure.
[0018] The method for preparing the precursor compounds of the invention can be conducted in standard batch or continuous mode reactors. One of ordinary skill in the art would recognize the scale and type of reactors which could be utilized in the context of the reagents and products so produced.
[0019] Compounds of the formulae (I) and (II) are useful as precursors in the formation of silicon-containing films on the surface of a microelectronic device by methods such as atomic layer deposition (see for example, U.S. Patent Nos. 10,580,645 and 10,424,477, incorporated herein by reference). Also, by way of example, compounds of formulae (I) and (II) can be introduced into a deposition chamber for the purposes of thermal CVD or ALD, or for the purposes of performing plasma-enhanced ALD or CVD. In these cases, a co-reactant gas can be introduced to deposit an SiO2 film, via oxidation in an oxidizing environment with O2, O3, N2O, or mixtures thereof. Similarly, compounds of formulae (I) and (II) can be introduced into a deposition chamber for the purposes of thermal CVD or ALD, or for the purposes of performing plasma-enhanced ALD or CVD. In these cases, a co-reactant gas can be introduced to deposit a silicon nitride film, via nitridation with N2, NH3, hydrazine or alkylhydrazine containing mixtures. The deposited films serve as dielectric layers within the microelectronic device. Examples
Example 1: Diiodo silane
[0020] A 25.0 g (143 mMol) sample of bis(diethylamino)silane was combined with 4 equivalents, 133.0 g (574 mMol) of benzoyl iodide and 500 mL of hexanes. The reaction was allowed to proceed for 2 hours, after which time, the desired diiodosilane product was detected by 'H NMR and all starting material was consumed. In the case of addition of benzoyl iodide to bis(diethylamino)silane, the observed yield was 7% (determined from concentration in hexanes). In the case of addition of bis(diethylamino)silane to benzoyl iodide, the observed yield was 3.5% (determined from concentration in hexanes). NMR samples were spiked to confirm with diiodosilane to confirm the identity of the signal.
Figure imgf000007_0001
Example 2: Diiodosilane
[0021] A 20.0 g (115 mMol) sample of bis(diethylamino)silane was combined with 4 equivalents, 78.0 g (459 mMol) of acetyl iodide and 400 mL of hexanes. The reaction was allowed to proceed for 10 minutes, after which time, trace amounts of the desired diiodosilane product was detected by 'H NMR and all starting material was consumed. Upon attempted isolation, decomposition of the product occurred. In the case of addition of acetyl iodide to bis(diethylamino)silane, the observed isolated yield was 0%.
Figure imgf000007_0002
Example 3: Diiodosilane
[0022] A 0.68 g (3.9 mMol) sample of bis(diethylamino)silane was combined with 4 equivalents, 4.69 g (15.6 mMol) of 2-fluorobenzoyl iodide and 10 mL of hexanes. The reaction was allowed to proceed for 10 minutes, after which time, 43% conversion of the desired diiodosilane product was detected by 'H NMR and all starting material was consumed. After an additional, 20 hr of stirring, the case of addition of 2-fluorobenzoyl iodide to bis(diethylamino) silane, the observed yield was 20%.
Figure imgf000007_0003
Example 4: Diiodosilane
[0023] A 0.27 g (1.6 mMol) sample of bis(diethylamino)silane was combined with 4 equivalents, 2.3 g (6.2 mMol) of 3,5-difluorobenzoyl iodide and 5 mL of hexanes. The reaction was allowed to proceed for 10 minutes, after which time, 81% conversion of the desired diiodosilane product was detected by 'H NMR and all starting material was consumed. After an additional, 20 hr of stirring, the case of addition of 3,5-difluorobenzoyl iodide to bis(diethylamino) silane, the observed yield was 20%.
Figure imgf000008_0001
Example 5 Diiodosilane
[0024] A 3.3 g (18.9 mMol) sample of bis(diethylamino)silane was combined with 4 equivalents, 1.0 g (4.7 mMol) of 2,2-dimethylpropanoyl iodide and 3 mL of hexanes. The reaction was allowed to proceed for 10 minutes, after which time, 20% of the desired diiodosilane product was detected by 1H NMR with 72% of the starting material remaining. After an additional, 20 hr of stirring, the case of addition of 2,2-dimethylpropanoyl iodide to bis(diethylamino)silane, the observed yield was 0.1%.
Figure imgf000008_0002
Aspects
[0025] In a first aspect, the disclosure provides a method for preparing a compound having the formula (I):
Figure imgf000008_0003
wherein x is 1 or 2, y is 2 or 3, and the sum of x plus y is 4, the method comprising: contacting a compound of the formula (A):
Figure imgf000008_0004
wherein (i) each R1 and each R2 is independently chosen from a C1-C6 alkyl group, a C3-C8 cycloaliphatic group, or hydrogen, or (ii) R1 and R2 are taken together with the nitrogen atom to which they are bonded to form a C4-C7 nitrogen-containing saturated or aromatic ring, provided that no more than one of R1 and R2 is hydrogen; with a compound of the formula:
Figure imgf000009_0001
wherein R3 is chosen from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (I).
[0026] In a second aspect, the disclosure provides the method of the first aspect, wherein the compound of formula (I) is
Figure imgf000009_0002
[0027] In a third aspect, the disclosure provides the method of the first aspect, wherein the compound of formula (I) is HSiR.
[0028] In a fourth aspect, the disclosure provides the method of the first or second aspect, wherein R1 and R2 are chosen from methyl, ethyl, propyl, sec-butyl, and t-butyl.
[0029] In a fifth aspect, the disclosure provides the method of any one of the first through fourth aspects, wherein at least one of R1 and R2 is t-butyl.
[0030] In a sixth aspect, the disclosure provides the method of the first, second, or third aspects, wherein at least one of R1 and R2 is cyclohexyl.
[0031] In a seventh aspect, the disclosure provides the method of the first, second, or third aspects, wherein R1 and R2 are taken together with the nitrogen atom to which they are attached, to form a pyrrole, pyrrolidine, or piperidine ring.
[0032] In an eighth aspect, the disclosure provides the method of any one of the first through the seventh aspects, wherein R3 is C1-C6 alkyl.
[0033] In a ninth aspect, the disclosure provides the method of any one of the first through seventh aspects, wherein R3 is phenyl. [0034] In a tenth aspect, the disclosure provides the method of any one of the first through seventh aspects, wherein R3 is substituted phenyl.
[0035] In an eleventh aspect, the disclosure provides the method of any one of the first through seventh, or tenth aspects, wherein R3 is 4-fluorophenyl.
[0036] In a twelfth aspect, the disclosure provides the method of any one of the first through seventh or tenth aspects, wherein R3 is 3,5-difluorophenyl.
[0037] In a thirteenth aspect, the disclosure provides the method of the first, second, or third aspects, wherein at least one of R1 and R2 is ethyl and R3 is methyl or phenyl.
[0038] In a fourteenth aspect, the disclosure provides a method for preparing a compound having the formula (II):
(H)z(I)ySi-Si(I)y(H)z (II) wherein y is 2 or 3, z is 0 or 1, and the sum of y and z is 3, the method comprising: contacting a compound of the formula (B):
Hz((R1)(R2)N)ySi-Si(N(R2)(R1))yHz (B); wherein (i) each R1 and each R2 is independently chosen from a C1-
C6 alkyl group, a C3-C8 cycloaliphatic group, or hydrogen, or (ii) R1 and R2 are taken together with the nitrogen atom to which they are bonded to form a C4-C7 nitrogen-containing saturated or aromatic ring, provided that no more than one of R1 and R2 is hydrogen; with a compound of the formula:
Figure imgf000010_0001
wherein R3 is chosen from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (II).
[0039] In a fifteenth aspect, the disclosure provides the method of the fourteenth aspect, wherein R1 and R2 are chosen from methyl, ethyl, propyl, sec-butyl, and t-butyl.
[0040] In a sixteenth aspect, the disclosure provides the method of the fourteenth aspect, wherein at least one of R1 or R2 is t-butyl.
[0041] In a seventeenth aspect, the disclosure provides the method of the fourteenth aspect, wherein at least one of R1 or R2 is cyclohexyl.
[0042] In an eighteenth aspect, the disclosure provides the method of the fourteenth aspect, wherein R1 and R2 are taken together with the nitrogen atom to which they are attached, to form a pyrrole, pyrrolidine, or piperidine ring.
[0043] In a nineteenth aspect, the disclosure provides the method of any one of the fourteenth through eighteenth aspects, wherein R3 is C1-C6 alkyl.
[0044] In a twentieth aspect, the disclosure provides the method of any one of the fourteenth through eighteenth aspects, wherein R3 is phenyl.
[0045] In a twenty-first aspect, the disclosure provides the method of the fourteenth aspect, wherein at least one of R1 and R2 is ethyl and R3 is methyl or phenyl.
[0046] Having thus described several illustrative embodiments of the present disclosure, those of skill in the art will readily appreciate that yet other embodiments may be made and used within the scope of the attached claims. Numerous advantages of the disclosure covered by this document have been set forth in the foregoing description. It will be understood, however, that this disclosure is, in many respects, only illustrative. Changes may be made in details without exceeding the scope of the disclosure. The disclosure’s scope is, of course, defined in the language in which the appended claims are expressed.

Claims

What is claimed is:
1. A method for preparing a compound having the formula (I):
Figure imgf000012_0001
wherein x is 1 or 2, y is 2 or 3, and the sum of x plus y is 4, the method comprising: contacting a compound of the formula (A):
Figure imgf000012_0002
wherein (i) each R1 and each R2 is independently chosen from a Ci- C3 alkyl group, a C3-C8 cycloaliphatic group, or hydrogen, or (ii) R1 and R2 are taken together with the nitrogen atom to which they are bonded to form a C4-C7 nitrogen-containing saturated or aromatic ring, provided that no more than one of R1 and R2 is hydrogen; with a compound of the formula:
Figure imgf000012_0003
wherein R1 is chosen from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (I).
2. The method of claim 1, wherein the compound of formula (I) is H2SiI2.
3. The method of claim 1, wherein the compound of formula (I) is HSiI.3.
4. The method of claim 1, wherein R1 and R2 are chosen from methyl, ethyl, propyl, sec-butyl, and t-butyl.
5. The method of claim 1, wherein at least one of R1 and R2 is t-butyl.
6. The method of claim 1, wherein at least one of R1 and R2 is cyclohexyl.
7. The method of claim 1, wherein R1 and R2 are taken together with the nitrogen atom to which they are attached, to form a pyrrole, pyrrolidine, or piperidine ring.
8. The method of claim 1, wherein R3 is C1-C6 alkyl.
9. The method of claim 1, wherein R3 is phenyl.
10. The method of claim 1, wherein R3 is substituted phenyl.
11. The method of claim 10, wherein R3 is 4-fluorophenyl.
12. The method of claim 10, wherein R3 is 3,5-difluorophenyl.
13. The method of claim 1, wherein at least one of R1 and R2 is ethyl and R3 is methyl or phenyl.
14. A method for preparing a compound having the formula (II):
(H)z(I)ySi-Si(I)y(H)z (II) wherein y is 2 or 3, z is 0 or 1, and the sum of y and z is 3, the method comprising: contacting a compound of the formula (B):
Hz((R1)(R2)N)ySi-Si(N(R2)(R1))yHz (B); wherein (i) each R1 and each R2 is independently chosen from a C1-C6 alkyl group, a C3-C8 cycloaliphatic group, or hydrogen, or (ii) R1 and R2 are taken together with the nitrogen atom to which they are bonded to form a C4-C7 nitrogen-containing saturated or aromatic ring, provided that no more than one of R1 and R2 is hydrogen; with a compound of the formula:
Figure imgf000014_0001
wherein R3 is chosen from C1-C6 alkyl, C1-C6 substituted alkyl, benzyl, substituted benzyl, biphenyl, naphthyl, phenyl, or substituted phenyl, to produce a compound of formula (II).
15. The method of claim 14, wherein R1 and R2 are chosen from methyl, ethyl, propyl, sec-butyl, and t-butyl.
16. The method of claim 14, wherein at least one of R1 or R2 is t-butyl.
17. The method of claim 14, wherein at least one of R1 or R2 is cyclohexyl.
18. The method of claim 14, wherein R1 and R2 are taken together with the nitrogen atom to which they are attached, to form a pyrrole, pyrrolidine, or piperidine ring.
19. The method of claim 14, wherein R3 is C1-C6 alkyl.
20. The method of claim 14, wherein R3 is phenyl.
21. The method of claim 14, wherein at least one of R1 and R2 is ethyl and R3 is methyl or phenyl.
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