US20180162881A1 - Highly reactive metal hydrides, process for their preparation and use - Google Patents

Highly reactive metal hydrides, process for their preparation and use Download PDF

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Publication number
US20180162881A1
US20180162881A1 US15/563,229 US201615563229A US2018162881A1 US 20180162881 A1 US20180162881 A1 US 20180162881A1 US 201615563229 A US201615563229 A US 201615563229A US 2018162881 A1 US2018162881 A1 US 2018162881A1
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metal
group
alkaline earth
highly reactive
valence
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Inventor
Ulrich Wietelmann
Christopher Kurth
Stefan Scherer
Peter Rittmeyer
Armin Stoll
Uwe Lischka
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Albemarle Germany GmbH
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Albemarle Germany GmbH
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    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/069—Aluminium compounds without C-aluminium linkages
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/02—Lithium compounds
    • 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
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/04—Sodium compounds
    • 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
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02—Magnesium compounds
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof

Definitions

  • the subject matter of the present patent specification relates to a powdery, highly reactive alkali and alkaline earth hydride compounds and to mixtures with elements of the 3rd main group of the periodic table of elements (PTE) and to the preparation thereof by reacting alkali or alkaline earth metals in the presence of finely dispersed metals or compounds of the third main group of the PTE, wherein the latter have one or more hydride ligands or said hydride ligands are converted in situ, under the prevailing reaction conditions, i.e., in the presence of hydrogen gas or another H source, into hydride species, and to the use thereof for the preparation of complex hydrides and organometal hydrides.
  • PTE periodic table of elements
  • the hydrides of the metals of the 1st and 2nd group of the PTE belong to the salt-type ionic compounds and are prepared as a rule by reacting the metal in question with hydrogen at elevated temperatures and under hydrogen atmosphere (P. Rittmeyer, U. Wietelmann, Ullmann's Encyclopedia of Industrial Chemistry, VCH Weinheim, Vol. A 13, 1989).
  • the highly stable lithium hydride is synthesized at 700-900° C. under 1 bar hydrogen atmosphere in the melt.
  • the melt is cooled and the solidified hydride is broken and ground.
  • Sodium hydride is also produced in the molten state in a high boiling oil at 250-300° C. under hydrogen.
  • Magnesium hydride is synthesized from powdery magnesium at 300-400° C. under an H 2 pressure of 100-150 bar.
  • the hydrogen donor is preferably selected from the group consisting of hydrogen, deuterium, tritium, ether, cyclohexadiene, cyclohexene.
  • a transition metal catalyst for example, FeCb
  • a polycyclic aromatic compound for example, naphthalene, phenanthrene
  • LiH* and NaH* can be used for reducing hexene to hexane.
  • the disadvantage of the last-mentioned synthesis variant is that the synthesis mixtures formed are contaminated with a combination of transition metals and naphthalene.
  • Active magnesium hydride can be prepared by high-pressure hydrogenation of Grignard compounds at higher temperatures (71-150° C., 350 bar) according to
  • dialkylmagnesium compounds for example, dibutylmagnesium
  • MgH 2 * E. J. Setijadi, C. Boyer, Phys. Chem. Chem. Phys. 2012, 14, 11386-97. Due to the unfavorable conditions, the expensive Mg sources, and, in the case of the Grignard compounds, the unavoidable contamination with magnesium halides (MgX 2 ), this MgH 2 * formation method has not gained importance.
  • the active magnesium hydride MgH 2 * prepared in this manner is reacted with an olefin in the presence of a transition metal catalyst, which is a halogen compound of metals of subgroups IV to VIII of the PTE, preferably in THF in the temperature range of 0 to 200° C. and at a pressure of 1 to 300 bar.
  • a transition metal catalyst which is a halogen compound of metals of subgroups IV to VIII of the PTE
  • the object of the invention is to indicate a process which, starting with inexpensive, commercially available raw materials, under mild conditions and without the use of toxic transition metal catalysts (for example, chromium), enables the synthesis of reactive metal hydrides (MH n *) of the 1st and 2nd group of the periodic table.
  • the hydrides should be produced as directly as possible in a form useful for synthesis purposes (i.e., as powder or dispersions in a solvent) and have a sufficiently high reactivity so that they have a broad synthesis application range, that is to say they are capable of
  • acid compounds for example, CH acids
  • the object is achieved in that metals M of the first or second period of the PTE are reacted with a compound of general formula M 1 x [M 2 H 3+x ] b under inert gas (preferably argon according to Eq. 3) or optionally in the presence of hydrogen gas or another source of hydrogen, and in the presence of a finely dispersed reactive metal of the third main PTE group (M 2 * ) or of a compound with the more broadly written general formula M 1 x [M 2 (A 1 y A 2 z ) 3+x ] b according to (aq. 4)
  • M 1 an alkali metal (Li, Na, K, Rb, Cs), an alkaline earth metal (Be, Mg, Ca, Sr, Ba) or (applicable only to Eq. 4) an element from the group of the rare earths (Sc, Y, La, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu);
  • M 2 an element of the 3rd main group of the PTE selected from the B, Al, Ga, In;
  • n 1 or 2, corresponding to the valence of the metal M;
  • a 1 H or an alkyl group containing 1-18 C atoms, wherein the up to four A groups can be identical or different;
  • a 1 and A 2 can only mean H, i.e., the reaction occurs exclusively according to Eq. (3).
  • a suspension then forms, which contains a highly reactive metal hydride MH n * in the mixture with q/6 equivalents (eq.) of highly reactive metal M 2 * and p/6 of highly reactive metal hydride M 1 H m *.
  • M 1 and M are identical.
  • the combinations LiAlH 4 and Li or NaAlH 4 and Na are particularly preferable.
  • LiAlH 4 can be used in catalytic quantities:
  • the mixtures of highly reactive metal M 2* and of the highly reactive metal hydride MH n *, which are prepared according to the invention, can be used directly as suspensions for subsequent reactions. It is also possible to remove the solvent largely or completely and thus prepare highly reactive powdery mixtures of M 2* and MH n *.
  • the solvent-free, highly reactive products when in contact with air, turn out to be pyrophoric and consequently have to be handled exclusively in a vacuum or under inert gas conditions (preferably under argon).
  • Reaction equation (4) applies to the case of an approximately stoichiometrically introduced hydrogen quantity; in the case of a hypostoichiometric reaction procedure or in the case of insufficiently long reaction times, elemental or only partially hydrogenated metal M 2 can remain.
  • the compound M 1 x [M 2 (A 1 y A 2 z ) 3+x ] b is needed only in catalytic quantities.
  • the compound M 1 x [M 2 (A 1 y A 2 z ) 3 ⁇ x ] b is used in catalytic quantities from 0.001 to 20 mol %, preferably from 0.01 to 10 mol %, with respect to the metal M.
  • This reaction procedure requires the use of a highly reactive metal grade M 2 * , preferably finely dispersed or amorphous aluminum.
  • the highly reactive M 2 must have a mean particle size D 50 between 0.01 and 100 ⁇ m and it must not be affected by previous contact with air, oxygen, moisture and other reactive substances with regard to its reactivity.
  • an industrial available metal grade for example, aluminum metal powder or aluminum metal shavings, can also be used.
  • transition metal catalysts for example, Ti, V, Fe
  • high H 2 pressures at least 10, preferably at least 50 bar. Since very fine/amorphous metal powders are not commercially available and high-pressure installations are relatively cost intensive, this variant is less preferable. It is thus simpler and more cost effective to use, as hydrogen transfer auxiliaries, the compounds represented by the generic formula M 1 x [M 2 (A 1 y A 2 z ) 3+x ] b in catalytic quantities.
  • AlH 4 As stoichiometric hydrogenation agents or hydrogenation catalysts, it is preferable to use compounds of aluminum M 1 x [Al(A 1 y A 2 z ) 3+x ] b or highly reactive/activated aluminum metal Al*.
  • the alkali alanates LiAlH 4 and NaAlH 4 which are prepared on the industrial scale, are particularly suitable. Alane AlH 3 can also be used with equal success.
  • the finely dispersed Al* or a forming reactive Al alloy reacts readily with hydrogen to form aluminum-containing hydrides, for example, AlH 3 .
  • the latter in turn can transfer the hydrogen under mild conditions to base metals M.
  • reactive elemental aluminum metal forms in addition to LiAlCl 4 .
  • the aluminates such as Li[AlEt 4 ] can react with hydrogen to form hydride-containing species.
  • the hydrogenation of the metals M according to equations (3) - (5) is carried out preferably in the presence of an anhydrous organic solvent.
  • Suitable as such a solvent are ethers (open-chain or cyclic, such as diethyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, tetrahydropyrane, dioxane, dioxolane and others), tertiary amines (triethylamine, tributylamine, morpholine, etc.), hydrocarbons (saturated C 4 -C 18 , preferably pentanes, hexanes, heptanes, octanes, etc.; aromatic compounds such as benzene, toluene, ethylbenzene, xylenes, cumene, etc.) in pure form or as any mixtures of at least two of the solvent
  • reaction temperatures can vary within broad limits, as a rule they are between ⁇ 20 and 150° C., preferably 0 and 100° C., and particularly preferably between 25 and 70° C. If a reaction procedure according to (4) or (5) is intended, then contact with elemental hydrogen must be ensured. Frequently an unpressurized mode of operation is sufficient; however, in order to achieve the shortest reaction times possible, it is possible to work under H 2 pressure conditions. Preferably, the H 2 excess pressure is 2-300 bar, particularly preferably 10-100 bar. It is also possible to use, as hydrogen source, a compound which releases hydrogen under selected operating conditions. Examples of this are: 1,3-cyclohexadiene, decalin, N-ethylcarbazole.
  • metal hydride aluminates for example, LiAlH 4 , NaAlH 4 , KAlH 4 and/or alane AlH 3 are preferably used.
  • mixed alanates such as Na[H 2 Al(O(CH 2 )2OCH 3 ) 2 ], Na[H 2 Al(C 2 H 5 ) 2 ] or mixed alanes such as HAl(C 4 H 9 ) 2 or H 2 AlC 4 H 9 can also be used.
  • the products according to the invention are produced in finely dispersed, in part nano-scale form. They are extremely reactive with respect to air and water, frequently even pyrophoric (i.e., they ignite spontaneously when air enters). Consequently, they have to be handled and stored with exclusion of reactive gases, i.e., in a vacuum, under nitrogen or inert gas atmosphere.
  • the products according to the invention consist mainly of the highly reactive metal hydride MH n * and, depending on reaction management (Eq. 3 or 4 or an intermediate case), they contain different quantities of M 2 * and M 1 H m *.
  • the molar ratio between MH n *, M 2 * and M 1 H m * is 1:0.001 to q/6:0 to p/6, preferably 1:0.01 to q/6:0 to p/6.
  • the metal hydrogenations are carried out according to Equations (3)-(5) in the presence of Lewis acids or unsaturated compounds that can be hydrometalated. These compounds are subsumed below under the term MH n * acceptors.
  • the residues R, R 1 , R 2 , R 3 , R 4 are any unbranched, cyclic or branched alkyl groups containing 1 to 12 C atoms.
  • preferable raw materials R3B for (Eq. 7) are: tri-sec-butylborane, trisiamylborane, tricyclohexylborane,
  • Al(OR)3 for (Eq. 8) are: aluminum trimethylate, aluminum tri(tert-butylate), aluminum tri(tert-pentylate), and
  • olefins with internalized double bonds for example, 2-butene, 2-pentene, 2-hexene, 2-heptene, 2-octene, 2-decene can also be accessed by the hydrolithiation reaction according to the invention.
  • Variant A the MH n * acceptor is added partially or completely before the start of the metal hydride formation to the mixture of the metal powder M and an aprotic solvent or solvent mixture. Then, the reagent M 1 x [M 2 (A 1 y A 2 z ) 3+x ] b used for the H transfer is added in stoichiometric quantity or as a catalyst. In the latter case, the reaction mixture is moreover brought in contact with a hydrogen source, most simply with elemental hydrogen.
  • Variant B the highly reactive metal hydrides MH n * are formed partially or completely according to reaction equations (2)-(4), and it is only then that the MH n * acceptor is added.
  • the hydrometalation reaction according to Eq. (9) can be accelerated by the addition of catalytically active transition metal compounds.
  • the halogen or alkoxy compounds of the 4th and 5th subgroup of the PTE can be considered, in particular the chlorides of Ti, Zr, Hf, V, Nb, Ta, preferably TiCl 4 , ZrCl 4 and VCl3, as well as metallocene compounds of the mentioned metals such as, for example, Cp 2 TiCl 2 , CpTiCl 3 , Cp 2 ZrCl 2 , or other complex compounds of the mentioned metals. They are added in quantities from 0.001 to 10 mol %, preferably 0.005 to 5 mol % with respect to metal hydride MH n *.
  • the black solid formed was isolated and dried.
  • the solid formed was isolated using a Schlenk frit.

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DE102015206894 2015-04-16
DE102015206894.3 2015-04-16
PCT/EP2016/056535 WO2016156195A2 (de) 2015-04-02 2016-03-24 Hochreaktive metallhydride, verfahren zu deren herstellung und anwendung

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EP (1) EP3277624B1 (de)
JP (1) JP6905507B2 (de)
KR (1) KR102557065B1 (de)
CN (1) CN107995905B (de)
AU (1) AU2016239913B2 (de)
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CN110116990B (zh) * 2019-04-10 2020-10-23 浙江大学 一种纳米氢化镁的原位制备方法
CN114132906B (zh) * 2022-01-04 2023-09-22 浙江大学 一种纳米氮氢化物及其原位制备方法和应用

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AU2016239913B2 (en) 2020-08-27
EP3277624A2 (de) 2018-02-07
DE102016204927A1 (de) 2016-10-06
KR102557065B1 (ko) 2023-07-18
CA2984691A1 (en) 2016-10-06
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WO2016156195A2 (de) 2016-10-06
JP2018516228A (ja) 2018-06-21
US11292804B2 (en) 2022-04-05
CN107995905A (zh) 2018-05-04
AU2016239913A1 (en) 2017-11-16
EP3277624B1 (de) 2020-05-06

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