WO1988003532A1 - Catalytic conversion of alkanes - Google Patents

Catalytic conversion of alkanes Download PDF

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Publication number
WO1988003532A1
WO1988003532A1 PCT/AU1987/000377 AU8700377W WO8803532A1 WO 1988003532 A1 WO1988003532 A1 WO 1988003532A1 AU 8700377 W AU8700377 W AU 8700377W WO 8803532 A1 WO8803532 A1 WO 8803532A1
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Prior art keywords
ligand
formula
alkyl
group
metal
Prior art date
Application number
PCT/AU1987/000377
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French (fr)
Inventor
Leslie David Field
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The University Of Sydney
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Publication date
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Publication of WO1988003532A1 publication Critical patent/WO1988003532A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/121—Metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
    • C07C5/50—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with an organic compound as an acceptor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron

Definitions

  • the present invention relates to the catalytic conversion of alkanes using a metal hydride complex as the catalyst, and to the novel alkyl metal hydride complexes produced.
  • one aspect of the present invention provides a method for the catalytic conversion of alkanes which comprises
  • M is a metal or metal ion selected from Group VIII of the Periodic Table
  • L 1 to L 4 may be the same or different and are selected from ligands of the formula (II), or bridged ligand wherein two of L 1 to L 4 form a ligand of formula (III), and a bridged ligand. wherein three of L 1 to L 4 form a ligand of formula (IV):
  • R is a lower alkyl group or a halo-substituted alkyl group or an alkoxy group or a halo-substituted alkoxy group and "n" is an integer from 1 to 4,
  • a second aspect of the invention provides novel alkyl metal hydride complexes where one or more (but not all) H atoms in Formula IA or IB are replaced by R 1 where R 1 is a C 1 -C 20 straight or branched alkyl or cycloalkyl group.
  • the catalytic cycle can be summarised as follows C
  • decomposition of the alkyl metal hydride intermediate may be carried out under conditions such as to liberate other alkane-derivatives, such as alcohols, alkyl halides or aldehydes.
  • the alkane is a C 1 -C 20 straight or branched alkyl or cycloalkyl group, particularly C 1 -C 10 alkanes such as methane, ethane, propane, butane, pentane, cyclopentane, hexane and cyclohexane.
  • the alkane is bonded to the metal via the terminal carbon atom.
  • a hydrogen atom must be present in the position beta to the metal to allow beta-hydride elimination to occur.
  • the complex is usually a neutral complex, which assists solubility in the alkane, but in other circumstances might be a charged complex.
  • M is selected from group VIII of the Periodic Table (comprising Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt).
  • the metal is Fe, Co, Ru or Rh.
  • Fe is preferred.
  • the R group is preferably a lower alkyl group, particularly a C 1 -C 4 alkyl.
  • R is preferably methyl, ethyl or propyl.
  • the integer n is preferably 2 or 3.
  • the R group is halo-substituted the or each substituent is preferably fluoro.
  • reaction of the alkane with the catalyst in step (i) may occur spontaneously, or may be brought about by heating, or by the use of a coupled chemical reaction, or most usually by irradiation with visible or UV light.
  • Decomposition of the alkyl metal hydride complex in step (ii) may be brought about in the same way but generally proceeds spontaneously.
  • the reaction is carried out in solution of the liquid or liquified alkane, if necessary at reduced temperature.
  • the catalyst may be supported on a solid support, for example by bonding to a solid polymer, and the alkane in liquid or gaseous form may be passed over the catalyst.
  • Decomposition of the alkyl metal hydride in the presence of OH or halide donor groups has the potential to produce alcohols and alkyl halides.
  • the alkene produced may be isolated or used directly in subsequent conversions for which they are basic starting materials for example, in the presence of a polymerisation catalyst the alkene may be polymerised in situ to a polyalkane.
  • Irradiation was carried out as follows. Samples containing 2-4mg FeH 2 (DMPE) 2 , in 0.4-0.8ml of solvent, were irradiated in pyrex tubes, positioned ca. 10cm from a 125 watt mercury vapour lamp. The tubes were supported within a quartz cylinder, and cooled by a stream of nitrogen gas.
  • DMPE FeH 2
  • Example 3 Irradiation of the complex Fe(DMPE) 2 H 2 in cyclopentane solution in the same manner as described in Example 1 produces cyclopentene in solution.
  • Example 4 Irradiation of the complex Fe(DMPE) 2 H 2 in pentane at -80°C in a manner as described in Example 1 produced the complex HFe(DMPE) 2 (n-pentyl) in 70% yield after 60% conversion.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

Alkanes are converted to alkenes in the presence of a metal dihydride or trihydride complex catalyst of formula (IA) or (IB), where M is a metal or metal ion selected from Group VIII of the Periodic Table, L1 to L4 may be the same or different and are selected from a ligand of formula (II), a bridged ligand wherein two of L1 to L4 form a ligand of formula (III), and a bridged ligand wherein three of L1 to L4 form a ligand of formula (IV), where R is a lower alkyl group or a halo-substituted alkyl group or an alkoxy group or a halo-substituted alkoxy group and ''n'' is an integer from 1 to 4, so as to liberate hydrogen and produce an alkyl metal hydride complex; and the alkyl metal hydride complex formed is decomposed to regenerate the metal hydride complex and liberate the alkene or alkane derivative. The iron complex is particularly preferred.

Description

CATALYTIC CONVERSION OF ALKANES TECHNICAL FIELD The present invention relates to the catalytic conversion of alkanes using a metal hydride complex as the catalyst, and to the novel alkyl metal hydride complexes produced.
BACKGROUND ART To our knowledge, the catalytic conversion of simple alkanes to alkenes has not been previously demonstrated. Such a process has great commercial potential for the production of alkene feed stocks e.g. propylene, butylene etc. required in industry for the production of polymers .
INVENTION It has now been surprisingly discovered that certain metal hydride complexes have the ability to react with alkanes to form an intermediate alkyl metal hydride, which can be decomposed to produce alkenes and/or other alkane derivatives.
In particular, one aspect of the present invention provides a method for the catalytic conversion of alkanes which comprises
(i) reacting an alkane with a metal dihydride or trihydride complex catalyst of the formula
Figure imgf000003_0001
where
M is a metal or metal ion selected from Group VIII of the Periodic Table,
L1 to L4 may be the same or different and are selected from ligands of the formula (II), or bridged ligand wherein two of L1 to L 4 form a ligand of formula (III), and a bridged ligand. wherein three of L1 to L4 form a ligand of formula (IV):
Figure imgf000004_0001
where
R is a lower alkyl group or a halo-substituted alkyl group or an alkoxy group or a halo-substituted alkoxy group and "n" is an integer from 1 to 4,
so as to liberate hydrogen and produce an alkyl metal hydride complex; and
(ii) decomposing the alkyl metal hydride complex to regenerate the metal hydride complex and liberate the alkene or alkane derivative. A second aspect of the invention provides novel alkyl metal hydride complexes where one or more (but not all) H atoms in Formula IA or IB are replaced by R1 where R1 is a C1-C20 straight or branched alkyl or cycloalkyl group. The catalytic cycle can be summarised as follows C
Figure imgf000005_0001
This illustrates the production of alkenes. However, decomposition of the alkyl metal hydride intermediate may be carried out under conditions such as to liberate other alkane-derivatives, such as alcohols, alkyl halides or aldehydes.
The alkane is a C1-C20 straight or branched alkyl or cycloalkyl group, particularly C1-C10 alkanes such as methane, ethane, propane, butane, pentane, cyclopentane, hexane and cyclohexane. Generally, the alkane is bonded to the metal via the terminal carbon atom. For the production of alkenes, a hydrogen atom must be present in the position beta to the metal to allow beta-hydride elimination to occur.
The complex is usually a neutral complex, which assists solubility in the alkane, but in other circumstances might be a charged complex.
M is selected from group VIII of the Periodic Table (comprising Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt).
Preferably the metal is Fe, Co, Ru or Rh. For reasons of economy, Fe is preferred.
In the ligands L1 and L4, the R group is preferably a lower alkyl group, particularly a C1-C4 alkyl. R is preferably methyl, ethyl or propyl. The integer n is preferably 2 or 3. Where the R group is halo-substituted the or each substituent is preferably fluoro.
The reaction of the alkane with the catalyst in step (i) may occur spontaneously, or may be brought about by heating, or by the use of a coupled chemical reaction, or most usually by irradiation with visible or UV light. Decomposition of the alkyl metal hydride complex in step (ii) may be brought about in the same way but generally proceeds spontaneously.
Preferably, the reaction is carried out in solution of the liquid or liquified alkane, if necessary at reduced temperature. Alternatively the catalyst may be supported on a solid support, for example by bonding to a solid polymer, and the alkane in liquid or gaseous form may be passed over the catalyst. Decomposition of the alkyl metal hydride in the presence of OH or halide donor groups has the potential to produce alcohols and alkyl halides. Similarly the alkene produced may be isolated or used directly in subsequent conversions for which they are basic starting materials for example, in the presence of a polymerisation catalyst the alkene may be polymerised in situ to a polyalkane.
EXAMPLES Embodiments of the invention will now be described by way of example only. Example 1
The complex Fe(DMPE)2H2, [DMPE=1,2-bis-(dimethylphosphino)ethane], synthesised by reduction of the corresponding dichloride with lithium aluminium hydride, was irradiated in a solution of pentane at -20°C. Hydrogen gas was evolved (confirmed by its characteristic signal in the 1HNMR spectrum of the reaction mixture). 1-Pentene was produced in the reaction mixture (confirmed by its characteristic signals in the 1H NMR spectrum and by trapping it as 1,2-dibromopentane on reaction with bromine). The intermediate cis-n-C5H11Fe(DMPE)2H was trapped, isolated and characterised as trans-n-C5H11Fe(DMPE)2Br.
Irradiation was carried out as follows. Samples containing 2-4mg FeH2(DMPE)2, in 0.4-0.8ml of solvent, were irradiated in pyrex tubes, positioned ca. 10cm from a 125 watt mercury vapour lamp. The tubes were supported within a quartz cylinder, and cooled by a stream of nitrogen gas. Example 2
Irradiation of the complex Fe(DMPE)2H2 in cyclopentane solution in the same manner as described in Example 1 produces cyclopentene in solution. Example 3
Irradiation of the complex Fe(DMPE)2H2 in hexane solution in the same manner as described in Example 1 produced 1-hexene in solution. Example 4 Irradiation of the complex Fe(DMPE)2H2 in pentane at -80°C in a manner as described in Example 1 produced the complex HFe(DMPE)2(n-pentyl) in 70% yield after 60% conversion. Treatment of the complex with bromine at
-80°C produced 1-bromopentane .

Claims

THE CLAIMS
1. A method for the catalytic conversion of alkanes which comprises (i) reacting a C1-C20 alkane with a metal dihydride or trihydride complex catalyst of the formula
Figure imgf000008_0001
where
M is a metal or metal ion selected from Group
VIII of the Periodic Table,
L1 to L4 may be the same or different and are selected from a ligand of the formula (II), a bridged ligand wherein two of L1 to L4 form a ligand of formula (III), and a bridged ligand wherein three of L1 to L4 form a ligand of formula (IV):
Figure imgf000008_0002
where
R is a lower alkyl group or a halo-substituted alkyl group or an alkoxy group or a halo-substituted alkoxy group and "n" is an integer from 1 to 4,
so as to liberate hydrogen and produce an alkyl metal hydride complex; and
(ii) decomposing the alkyl metal hydride complex to regenerate the metal hydride complex and liberate the alkene or alkane derivative.
2. A method according to claim 1 wherein the alkane is a C1-C10 straight or branched alkyl or cycloalkyl group.
3. A method according to claim 1 wherein M is selected from Fe, Co, Ru and Rh.
4. A method according to claim 3 wherein M is Fe.
5. A method according to claim 1 wherein the ligands L1 to L4 are constituted by two bridged ligands of formula (III) where n is 2 or 3 and R is C1-C4 alkyl.
6. A method according to claim 5 wherein the C1-C4 alkyl groups are substituted by one or more fluoro.
7. A method according to claim 1 conducted in the presence of ultraviolet light.
8. A method according to claim 1 wherein the catalyst is iron 1,2-bis-(dimethylphosphino)ethane dihydride. An alkyl metal hydride complex of formula
Figure imgf000010_0001
where at least one R1 is a C1-C20 straight or branched cycloalkyl group and at least one R1 is hydrogen; ligands L1 to L4 may be the same or different and are selected from a ligand of the formula (II), a bridged ligand wherein two of L1 to L4 form a ligand of formula (III), and a bridged ligand wherein three of L1 to L4 form a ligand of formula (IV):
Figure imgf000010_0002
where
R is a lower alkyl group or a halo-substituted alkyl group or an alkoxy group or a halo-substituted alkoxy group and "n" is an integer from 1 to 4.
PCT/AU1987/000377 1986-11-11 1987-11-10 Catalytic conversion of alkanes WO1988003532A1 (en)

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AUPH8903 1986-11-11
AU890386 1986-11-11

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3851009A (en) * 1971-05-06 1974-11-26 Phillips Petroleum Co Oxidative dehydrogenation processes
US3852369A (en) * 1971-05-06 1974-12-03 Phillips Petroleum Co Processes for dehydrogenation of hydrocarbons
US3870764A (en) * 1972-06-21 1975-03-11 Phillips Petroleum Co Oxidative dehydrogenation process
US3997579A (en) * 1975-10-15 1976-12-14 E. I. Du Pont De Nemours And Company Selected phosphorus complexes of zerovalent iron
GB1577101A (en) * 1977-02-24 1980-10-15 Anic Spa Palladium phosphine complexes and their production
US4397787A (en) * 1980-03-19 1983-08-09 The Procter & Gamble Company Rhodium complexes containing chiral phosphine ligands useful as hydrogenation catalysts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3851009A (en) * 1971-05-06 1974-11-26 Phillips Petroleum Co Oxidative dehydrogenation processes
US3852369A (en) * 1971-05-06 1974-12-03 Phillips Petroleum Co Processes for dehydrogenation of hydrocarbons
US3870764A (en) * 1972-06-21 1975-03-11 Phillips Petroleum Co Oxidative dehydrogenation process
US3997579A (en) * 1975-10-15 1976-12-14 E. I. Du Pont De Nemours And Company Selected phosphorus complexes of zerovalent iron
GB1577101A (en) * 1977-02-24 1980-10-15 Anic Spa Palladium phosphine complexes and their production
US4397787A (en) * 1980-03-19 1983-08-09 The Procter & Gamble Company Rhodium complexes containing chiral phosphine ligands useful as hydrogenation catalysts

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