Classifications

• • 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
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/5004—Acyclic saturated phosphines
  • C07F9/5009—Acyclic saturated phosphines substituted by B, Si, P or a metal
• • 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
  • C01B33/04—Hydrides of silicon

Definitions

• the present application is directed to heteroatom doped silane compounds and methods of producing such compounds.
• the methods commonly includes reacting a halogen substituted silane with a nucleophilic reagent to form a doped silane with a Si-E bond, where "E” may be selected from Group 13, Group 14, Group 15 and/or Group 16 elements.
• the doped silane is desirably a liquid under ambient temperature and pressure conditions (e.g., under 1 atmosphere pressure at 298 0 C).
• the halogen substituted silane may be formed by reacting a cyclic or acyclic silane with a halogenating reagent.
• the halogen substituted silane may be formed by reacting an aryl substituted (e.g., phenyl substituted) cyclic or acyclic silane with a hydrogen halide in the presence of a Lewis acid catalyst, such as AICI 3 .
• a Lewis acid catalyst such as AICI 3
• Monohalogen substituted cyclic silanes such as monochlorocyclopentasilane, monochlorocyclohexasilane, monobromocyclopentasilane and monobromocyclohexasilane, may be particularly desirable as intermediates for use in producing the present doped silane compounds.
• the present heteroatom doped silane compounds may have the formula:
• Examples of the present heteroatom doped silane compounds include cyclic silane compounds having the formula:
• n is an integer greater than 2 (commonly 3 to 10); m is 2n - 2 or 2n; and y is an integer from 1 to n.
• heteroatom doped silane compounds include acyclic silane compounds (e.g., branched and/or linear silanes), which are desirably a liquid under ambient temperature and pressure, having the formula:
• n H m -y(PH2)y wherein n is an integer greater than 2; m is 2n + 2; and y is an integer from 1 to n.
• Suitable synthetic intermediates which may be used to produce such heteroatom doped silane compounds include halogen substituted cyclic silane compounds having the formula: wherein n is an integer greater than 2 (commonly about 3 to 10); m is an integer from 2n - 2 to 2n; y is 1 or 2; and each X independently represents a halogen atom.
• the present heteroatom doped silane compounds may be prepared by reacting a mixture comprising:
• a solvent e.g., an ether solvent such as glyme, diglyme or the like.
• the halogenated silane may be reacted with a nucleophile of the formula:
• Suitable examples of such nucleophiles include NaPH 2 , LiPH 2 , NaAl(PH 2 ) 4 and LiAl(PH 2 ) 4 .
• the present application provides a method of producing a halogenated cyclic silane of the formula: wherein n is an integer greater than 2 (commonly about 3 to 10); m is 2n - 2 or 2n; y is 1 or 2; and each X independently represents a halogen atom.
• the method includes reacting a cyclic silane (e.g., either a monocyclic or bicyclic) with a halogenating agent to provide a halo-silane having a formula: Slnrim-y ⁇ X-y wherein n is an integer greater than 2 (commonly about 3 to 10; m is an integer from 2n - 2 to 2n; y is 1 or 2; and each X independently represents a halogen atom.
• suitable halogenating agents include AgCl, HgCl 2 , HgBr 2 , N-chlorosuccinimide (“NCS"), N-bromosuccinimide (“NBS”), SnCl 4 and iodine (I 2 ).
• heteroatom doped silane compounds may be prepared by reacting a mixture comprising: with other phosphorus-containing nucleophiles.
• halogenated silanes may be reacted with phosphorus-containing nucleophiles of the formula:
• M*PHSiH 3 where M* is an alkali metal (e.g., Li) to provide a heteroatom doped silane having a formula:
• heteroatom doped silane compounds may be prepared by reacting a mixture comprising: with phosphorus-containing nucleophiles of the formula:
• M*P(SiH 3 ) 2 where M* is an alkali metal (e.g., Li) to provide a heteroatom doped silane having a formula:
• Figure 1 depicts a GC-MS of the product solution produced according to the procedure described in Example 1.
• Figure 2 depicts GC-MS of the product solution produced according to the procedure described in Example 2.
• Figure 3 depicts GC-MS of the product solution produced according to the procedure described in Example 2 displaying Si-P bond formation.
• the present heteroatom doped silane compounds may be produced by reacting a halogen substituted silane with a nucleophilic reagent to form the doped silane.
• a halogenated silane may be reacted with a phosphorus-containing nucleophile to form a compound which includes a Si-P bond.
• the resulting product, a phosphorus doped silane is desirably a liquid under ambient temperature and pressure (e.g., under 1 atmosphere pressure at 298°C).
• the halogen substituted silane may be formed by reacting a cyclic or acyclic silane with a halogenating reagent.
• the starting materials, reaction conditions and/or stoichiometry may be controlled such that the reaction product is predominantly a silane substituted with only one or two halogen atoms.
• the halogenation reaction is typically carried out in the presence of a solvent, e.g., a chlorinated hydrocarbon solvent such as methylene chloride, chloroform, carbon tetrachloride and/or dichloroethane.
• the halogen substituted silane may be formed by dissolving a silane compound, e.g., a cyclic silane such as cyclotrisilane, cyclopentasilane or cyclohexasilane, in a chlorinated solvent (e.g., methylene chloride) and stirring the solution of silane with an inorganic halogenating reagent, such as AgCl, HgCl 2 , HgBr 2 , BCI 3 , or SnCl 4 . In such cases, an excess of the halogenating reagent may be used. After stirring the reaction mixture for a period of several hours, a mixture containing mono- and dihalogenated silane is typically obtained.
• a silane compound e.g., a cyclic silane such as cyclotrisilane, cyclopentasilane or cyclohexasilane
• a chlorinated solvent e.g., methylene chloride
• a silane compound e.g., a cyclic silane such as cyclotrisilane, cyclopentasilane or cyclohexasilane
• a chlorinated solvent e.g., methylene chloride or carbon tetrachloride
• NCS N- chlorosuccinimide
• NBS N-bromosuccinimide
• NBS or NCS are added to the solution for each mole of silane.
• dihalogenated silanes are the desired products
• two moles of NBS or NCS are added to the solution for each mole of silane.
• Suitable halogenated silane intermediates include: cyclotrisilane having 1 or 2 halogen atoms attached thereto; cyclopentasilane having 1 or 2 halogen atoms attached thereto; cyclohexasilane having 1 or 2 halogen atoms attached thereto; silylcyclopentasilane having 1 or 2 halogen atoms attached thereto; silylcyclohexasilane having 1 or 2 halogen atoms attached thereto; and spiro[4.4]nonasilane having 1 or 2 halogen atoms attached thereto.
• Halogenated silane compounds, which may be used to produce the present heteroatom doped silane compounds may be produced by reacting a halogenating reagent with a corresponding silane precursor.
• suitable halogenating reagents include:
• N-chlorosuccinimide N-chlorosuccinimide
• N-bromosuccinimide (“NBS").
• Suitable phosphorus-containing nucleophiles which may be used to produce the present heteroatom doped silane compounds include:
• LiHPSiH 3 LiP(SiH 3 ) 2 and LiAl(PHSiH 3 ) 4 .
• CH 2 Cl 2 methylene chloride
• NaAl(PH 2 ) 4 was synthesized by reacting 50.4 mg OfNaPH 2 (0.90 mmol, 1.00 eq) suspended in 2 mL of diethylene glycol dimethyl ether (diglyme) with 30.8 mg OfAlCl 3 (0.231 mmol, 3.90 eq) dissolved in 1 mL which resulted in the formation of a cloudy white slurry. This white precipitate is consistent with the formation of sodium chloride, NaCl.
• the AlCl 3 was quantitatively transferred by washing the vial with 3 x 1 mL of diglyme resulting in a 6 mL mixture that was allowed to stir overnight.
• One embodiment provides a method of preparing a doped silane which includes reacting a mixture comprising:
• MPH2 include:
• the method may include reacting Si n H 2n-y X y with
• a heteroatom doped silane compound may be formed by reacting a mixture, which includes:
• a heteroatom doped silane compound may be formed by reacting a mixture, which includes:
• Suitable examples of the present heteroatom doped silane compounds include doped silanes having a formula:
• the present heteroatom doped silane compounds may desirably include compounds having one or more of the following formulas:
• heteroatom doped silane compounds include doped cyclic silanes having a formula:
• n H m -y(PH2)y wherein n is an integer from 3 to 10; m is 2n - 2 or 2n; and y is an integer from 1 to n.
• n is an integer from 3 to 10; m is 2n - 2 or 2n; and y is an integer from 1 to n.
• Other examples of the present heteroatom doped silane compounds include doped silanes having a formula:
• heteroatom doped silane compounds include doped silanes having a formula:
• n is an integer greater than 2 (typically 3 to 10); m is an integer from 2n - 2 to 2n +
• y is an integer from 1 to n (and often desirably 1 or 2).
• Certain embodiments provide halogen substituted cyclic silanes having the formula:
• n is an integer greater than 2 (commonly 3 to 10); m is 2n or 2n - 2; y is 1 or 2; and each X independently represents a halogen atom.
• Suitable examples include: such halogen substituted cyclic silanes wherein n is 3; m is 6; y is 1; and X is a chlorine atom; such halogen substituted cyclic silanes wherein n is 5; m is 10; y is 1; and X is a chlorine atom; such halogen substituted cyclic silanes wherein n is 6; m is 12; y is 1; and X is a chlorine atom; or such halogen substituted cyclic silanes wherein n is 7; m is 14; y is 1; and X is a chlorine atom.
• halogen substituted cyclic silanes include: such halogen substituted cyclic silanes wherein n is 3; m is 6; y is 1; and X is a bromine atom; such halogen substituted cyclic silanes wherein n is 5; m is 10; y is 1; and X is a bromine atom; such halogen substituted cyclic silanes wherein n is 6; m is 12; y is 1; and X is a bromine atom; or such halogen substituted cyclic silanes wherein n is 7; m is 14; y is 1; and X is a bromine atom.
• Suitable halogen substituted cyclic silanes include: chlorocyclopentasilane and/or dichlorocyclopentasilane; chlorocyclohexasilane and/or dichlorocyclohexasilane; monochloro- and/or dichloro- derivatives of silylcyclohexasilane; monochloro- and/or dichloro- derivatives of silylcyclopentasilane; monochloro- and/or dichloro- derivative of spiro[4.4]nonasilane; silylcyclopentasilane having 1 and/or 2 chlorine substituents; spiro[4.4]nonasilane having 1 and/or 2 chlorine substituents; silylcyclohexasilane having 1 and/or 2 chlorine substituents; cyclohexasilane having 1 and/or 2 chlorine substituents; cyclopentasilane having 1 and/or 2 chlorine substituents;
• Suitable halogen substituted cyclic silanes include: bromocyclopentasilane and/or dibromocyclopentasilane; bromocyclohexasilane and/or dibromocyclohexasilane; monobromo- and/or dibromo- derivatives of silylcyclohexasilane; monobromo- and/or dibromo- derivatives of silylcyclopentasilane; monobromo- and/or dibromo- derivative of spiro[4.4]nonasilane; silylcyclopentasilane having 1 and/or 2 bromine substituents; spiro[4.4]nonasilane having 1 and/or 2 bromine substituents; silylcyclohexasilane having 1 and/or 2 bromine substituents; cyclohexasilane having 1 and/or 2 bromine substituents; cyclopentasilane having 1 and/

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• 2009
  • 2009-05-26 WO PCT/US2009/045132 patent/WO2009148878A2/en not_active Ceased
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