CN106698346A - Method for synthesizing anionic potassium hydroborate KB3H8 - Google Patents
Method for synthesizing anionic potassium hydroborate KB3H8 Download PDFInfo
- Publication number
- CN106698346A CN106698346A CN201710086428.6A CN201710086428A CN106698346A CN 106698346 A CN106698346 A CN 106698346A CN 201710086428 A CN201710086428 A CN 201710086428A CN 106698346 A CN106698346 A CN 106698346A
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- CN
- China
- Prior art keywords
- sylvite
- reaction
- hydride ion
- boron hydride
- kb3h8
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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
- 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
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
- C01B6/15—Metal borohydrides; Addition complexes thereof
- C01B6/19—Preparation from other compounds of boron
- C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a method for synthesizing anionic potassium hydroborate KB3H8 and belongs to the technical field of synthesis of hydroborates. The technical scheme of the invention is as follows: the method for synthesizing the anionic potassium hydroborate KB3H8 comprises the steps of adding potassium metal into a reaction vessel under anhydrous and oxygen-free conditions, then, adding a tetrahydrofuran solution of borane into the reaction vessel, and carrying out reaction at the temperature of 0 DEG C to 50 DEG C by stirring, thereby preparing a target product, i.e., the anionic potassium hydroborate KB3H8. According to the method, alkali metal is not dispersed with any medium any more, and the reaction is carried out by directly using potassium metal blocks, so that the method has the advantages of simplicity in operation, low toxicity, harmlessness, safety and reliability compared with the former methods, thereby being applicable to large-scale production.
Description
Technical field
The invention belongs to the synthesis technical field of hydroboron, and in particular to a kind of boron hydride ion sylvite KB3H8Conjunction
Into method.
Background technology
Anion B3H8 -Tool has been widely used, due to its hydrogen content higher, hydrogen storage field have it is very big should
With prospect, the hydrogen storage material NH for such as having synthesized4[B3H8]（Inorg. Chem. 2011, 50, 3738-3742）, containing big
The negative hydrogen of amount, and have good dissolubility in it common are machine solvent, therefore, it is possible to be used as reducing agent；And can be with
As the predecessor for synthesizing other boron-containing compounds, such as synthesis semi-conducting material MgB2Predecessor Mg (B3H8)2（Inorg.
Chem. 2007, 46, 9060-9066）.
Due to the limitation of synthetic method, M (B3H8)nClass hydroboron is not developed well.Therefore, one is found
Plant simple to operate, safety non-toxic and synthetic method with low cost is highly desirable to.Synthesize M (B at present3H8)nClass hydroboron
Method mainly have：
1st, using diborane and alkali metal, mainly sodium amalgam, NaB is generated3H8.Toxicity is used in method very big and very uneasy
Complete mercury, diborane etc..Harm of the mercury to human body is very big, and operation inconvenience.Diborane is extremely sensitive to air, inflammable and explosive,
And with severe toxicity, operation is same abnormally dangerous.
2nd, iodine aoxidizes sodium borohydride at 100 DEG C.Required solvent boiling point is higher at a temperature of this, expends the energy, and close
Into B3H8 -Anion contains except the solvent not fallen.
3rd, the tetrahydrofuran solution of sodium amalgam and borine（THF•BH3）Reaction.Equally exist lacking in the above method 1 and 2
Point.
4th, alkali metallic sodium is dispersed on silica gel at 150 DEG C, then the tetrahydrofuran with borine reacts.Divide at this temperature
Sodium is dissipated, operation is very inconvenient, and with the presence of danger very high.
5th, under conditions of ball milling, alkali metallic sodium is dispersed on inorganic salts, such as NaCl, CaCl2Deng equally existing above-mentioned side
Shortcoming in method 4.
In view of synthesizing M (B above3H8)nThe unfavorable factor of class hydroboron, it is necessary to which designing a kind of building-up process can
Avoid using the toxicity hazardous chemicals high such as mercury, diborane, and boron hydride ion sylvite KB simple to operate, safe and reliable3H8
Synthetic method.
The content of the invention
Present invention solves the technical problem that there is provided a kind of harmless boron hydrogen of simple to operate, safe and reliable and low toxicity it is cloudy from
Sub- sylvite KB3H8Synthetic method.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of boron hydride ion sylvite KB3H8Synthesis
Method, it is characterised in that：Metallic potassium is added in reaction vessel under conditions of anhydrous and oxygen-free, is subsequently adding the tetrahydrochysene of borine
Tetrahydrofuran solution, target product boron hydride ion sylvite KB is obtained in 0~50 DEG C of stirring reaction3H8。
Further preferably, described boron hydride ion sylvite KB3H8Synthetic method concretely comprise the following steps：In nitrogen glove
In case, metallic potassium is fitted into schlenk reaction bulbs, schlenk reaction bulbs are removed into glove box, Ran Houjia with after plug seal
Enter the tetrahydrofuran solution of the borine that molar concentration is 0.5~5mol/L（THF•BH3）, wherein metallic potassium and THF BH3Feed intake
Mol ratio is 1:2~1:4, in 0~50 DEG C of stirring reaction until metallic potassium is wholly absent, insoluble matter is filtered to remove, filtrate is concentrated
Remove solvent and obtain white sticky solid, again with toluene is washed for several times, then vacuum concentration removes solvent and obtains white pure
Boron hydride ion sylvite KB3H8Powder.
Boron hydride ion sylvite KB of the present invention3H8Synthetic method in reaction equation be：
2K + 4THF•BH3 = KB3H8 + KBH4 + 4THF。
Further preferably, the reaction temperature of building-up process is preferably room temperature.
The present invention has the advantages that compared with prior art：The present invention does not use any medium to disperse alkali gold
Category, is directly reacted with metallic potassium block, and more simple to operate than method before, low toxicity is harmless, safe and reliable, is adapted to scale
Production.
Brief description of the drawings
Fig. 1 is the boron hydride ion sylvite KB of the synthesis of the embodiment of the present invention 13H8In tetrahydrofuran11B and11B { H } liquid
Body nuclear-magnetism figure, obtained target product is pure KB as seen from the figure3H8。
Specific embodiment
The above of the invention is described in further details by the following examples, but this should not be interpreted as this
The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair
Bright scope.
Embodiment 1
All operations are carried out in a nitrogen atmosphere.In glove box, in the schlenk reaction bulbs of the 100mL equipped with magneton
0.78g metallic potassiums are added, schlenk reaction bulbs are removed into glove box with after plug seal.Molar concentration is subsequently adding for 1mol/
The tetrahydrofuran solution of the borine of L（THF•BH3）40mL, is stirred at room temperature reaction 8 hours.Insoluble matter is filtered to remove, will be filtered
Liquid concentration removes solvent and obtains white sticky solid, again with toluene washing solid 3 times, each 20mL, then vacuum concentration removing
Solvent obtains white solid product, the pure KB of as solvent-free adduction3H8.Resulting KB3H80.64g is weighed as, is calculated and is produced
Rate is 80%, and nuclear-magnetism detects its purity close to 100%.
Embodiment 2
All operations are carried out in a nitrogen atmosphere.In glove box, in the schlenk reaction bulbs of the 100mL equipped with magneton
0.78g metallic potassiums are added, schlenk reaction bulbs are removed into glove box with after plug seal.Molar concentration is subsequently adding for 1mol/
The tetrahydrofuran solution of the borine of L（THF•BH3）80mL, in 0 DEG C of stirring reaction 12 hours.Insoluble matter is filtered to remove, by filtrate
Concentration removes solvent and obtains white sticky solid, and then again with toluene washing solid 3 times, each 20mL is concentrated in vacuo removing molten
Agent obtains white solid product, the pure KB of as solvent-free adduction3H8.Resulting KB3H80.68g is weighed as, yield is calculated
It is 85%, nuclear-magnetism detects its purity close to 100%.
Embodiment 3
All operations are carried out in a nitrogen atmosphere.In glove box, in the schlenk reaction bulbs of the 100mL equipped with magneton
0.78g metallic potassiums are added, schlenk reaction bulbs are removed into glove box with after plug seal.Being subsequently adding molar concentration is
The tetrahydrofuran solution of the borine of 0.5mol/L（THF•BH3）80mL, is stirred at room temperature reaction 10 hours.It is filtered to remove insoluble
Thing, removes filtrate concentration solvent and obtains white sticky solid, and again with toluene washs solid 3 times, each 20mL, and then vacuum is dense
Contracting removes solvent and obtains white solid product, the pure KB of as solvent-free adduction3H8.Resulting KB3H8It is weighed as 0.68g,
It is 85% to calculate yield, and nuclear-magnetism detects its purity close to 100%.
Embodiment 4
All operations are carried out in a nitrogen atmosphere.In glove box, in the schlenk reaction bulbs of the 100mL equipped with magneton
0.78g metallic potassiums are added, schlenk reaction bulbs are removed into glove box with after plug seal.Molar concentration is subsequently adding for 5mol/
The tetrahydrofuran solution of the borine of L（THF•BH3）8mL, in 50 DEG C of stirring reactions 6 hours.Insoluble matter is filtered to remove, filtrate is dense
Contracting removes solvent and obtains white sticky solid, and then again with toluene washing solid 3 times, each 20mL is concentrated in vacuo and removes solvent
Obtain white solid product, the pure KB of as solvent-free adduction3H8.Resulting KB3H80.64g is weighed as, calculating yield is
80%, nuclear-magnetism detects its purity close to 100%.
Embodiment above describes general principle of the invention, principal character and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, simply original of the invention is illustrated described in above-described embodiment and specification
Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements each fall within
In the scope of protection of the invention.
Claims (3)
1. a kind of boron hydride ion sylvite KB3H8Synthetic method, it is characterised in that：By metallic potassium under conditions of anhydrous and oxygen-free
It is added in reaction vessel, is subsequently adding the tetrahydrofuran solution of borine, target product boron hydrogen is obtained in 0~50 DEG C of stirring reaction
Anion sylvite KB3H8。
2. boron hydride ion sylvite KB according to claim 13H8Synthetic method, it is characterised in that concretely comprise the following steps：
In nitrogen glove box, metallic potassium is fitted into schlenk reaction bulbs, schlenk reaction bulbs are removed into gloves with after plug seal
Case, is subsequently adding the tetrahydrofuran solution THF BH of the borine that molar concentration is 0.5~5mol/L3, wherein metallic potassium and THF
BH3Molar ratio be 1:2~1:4, in 0~50 DEG C of stirring reaction until metallic potassium is wholly absent, insoluble matter is filtered to remove,
Filtrate concentration is removed into solvent and obtains white sticky solid, again with toluene is washed for several times, and then vacuum concentration removes solvent and obtains
The pure boron hydride ion sylvite KB of white3H8Powder.
3. boron hydride ion sylvite KB according to claim 1 and 23H8Synthetic method, it is characterised in that：Building-up process
Reaction temperature be preferably room temperature.
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| CN201710086428.6A CN106698346B (en) | 2017-02-17 | 2017-02-17 | A kind of boron hydride ion sylvite KB3H8Synthetic method |
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| CN106698346A true CN106698346A (en) | 2017-05-24 |
| CN106698346B CN106698346B (en) | 2019-04-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098357A (en) * | 2017-06-10 | 2017-08-29 | 复旦大学 | A kind of preparation method of the boronic acid compounds of octahydro three |
| CN107473184A (en) * | 2017-08-02 | 2017-12-15 | 河南师范大学 | A kind of hydroboron LiB of lithium3H8Synthetic method |
| CN108358165A (en) * | 2018-03-10 | 2018-08-03 | 河南师范大学 | A kind of hydroboron sodium salt NaB3H8Preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417496A (en) * | 2014-09-23 | 2016-03-23 | 中国科学院大连化学物理研究所 | synthesis method for borohydride of sodium |
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2017
- 2017-02-17 CN CN201710086428.6A patent/CN106698346B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417496A (en) * | 2014-09-23 | 2016-03-23 | 中国科学院大连化学物理研究所 | synthesis method for borohydride of sodium |
Non-Patent Citations (1)
| Title |
|---|
| TARA G. HILL ET AL.: "Reduction of BH3•THF by Alkali Metal (K, Rb, Cs) and Ytterbium Mercury Amalgams To Form Salts of [B3H8]-: A Simple Procedure for the Synthesis of Tetraborane( 10)", 《INORG. CHEM》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098357A (en) * | 2017-06-10 | 2017-08-29 | 复旦大学 | A kind of preparation method of the boronic acid compounds of octahydro three |
| CN107098357B (en) * | 2017-06-10 | 2020-10-30 | 复旦大学 | Preparation method of octahydro-triboric acid compound |
| CN107473184A (en) * | 2017-08-02 | 2017-12-15 | 河南师范大学 | A kind of hydroboron LiB of lithium3H8Synthetic method |
| CN107473184B (en) * | 2017-08-02 | 2019-09-13 | 河南师范大学 | A kind of hydroboron LiB of lithium3H8Synthetic method |
| CN108358165A (en) * | 2018-03-10 | 2018-08-03 | 河南师范大学 | A kind of hydroboron sodium salt NaB3H8Preparation method |
| CN108358165B (en) * | 2018-03-10 | 2021-07-20 | 河南师范大学 | Sodium borohydride salt NaB3H8Preparation method of (1) |
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Granted publication date: 20190402 Termination date: 20200217 |