CN106698346B - A kind of boron hydride ion sylvite KB3H8Synthetic method - Google Patents
A kind of boron hydride ion sylvite KB3H8Synthetic method Download PDFInfo
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- CN106698346B CN106698346B CN201710086428.6A CN201710086428A CN106698346B CN 106698346 B CN106698346 B CN 106698346B CN 201710086428 A CN201710086428 A CN 201710086428A CN 106698346 B CN106698346 B CN 106698346B
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- sylvite
- boron hydride
- hydride ion
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- metallic potassium
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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
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- 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
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Abstract
The invention discloses a kind of boron hydride ion sylvite KB3H8Synthetic method, belong to the synthesis technical field of hydroboron.A kind of technical solution of the present invention main points are as follows: boron hydride ion sylvite KB3H8Synthetic method, metallic potassium is added in reaction vessel under conditions of anhydrous and oxygen-free, then be added borine tetrahydrofuran solution, obtained target product boron hydride ion sylvite KB is stirred to react in 0~50 DEG C3H8.The present invention does not use any medium to disperse alkali metal, is directly reacted with metallic potassium block, more easy to operate than method before, and low toxicity is harmless, securely and reliably, is suitble to large-scale production.
Description
Technical field
The invention belongs to the synthesis technical fields of hydroboron, and in particular to a kind of boron hydride ion sylvite KB3H8Conjunction
At method.
Background technique
Anion B3H8 -Tool has been widely used, and due to its higher hydrogen content, has very big answer in hydrogen storage field
With prospect, the hydrogen storage material NH such as synthesized4[B3H8] (Inorg. Chem. 2011,50,3738-3742), containing big
The negative hydrogen of amount, and have good dissolubility in common organic solvent, therefore can use as reducing agent；And it can be with
As the predecessor for synthesizing other boron-containing compounds, semiconductor material MgB is such as synthesized2Predecessor 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
Planting easy to operate, safe and non-toxic and low-cost synthetic method is highly desirable.Synthesis M (B at present3H8)nClass hydroboron
Method mainly have:
1, using diborane and alkali metal, mainly sodium amalgam, NaB is generated3H8.Toxicity has been used in method very greatly and very
Unsafe mercury, diborane etc..Mercury is very big to the harm of human body and inconvenient.Diborane is extremely sensitive to air, inflammable easy
It is quick-fried, and there is severe toxicity, operation is same abnormally dangerous.
2, iodine is in 100 DEG C of oxidation sodium borohydrides.Solvent boiling point needed at a temperature of this is higher, consuming energy, and closes
At B3H8 -Anion contains except the solvent not fallen.
3, tetrahydrofuran solution (the THF BH of sodium amalgam and borine3) reaction.Equally exist lacking in the above method 1 and 2
Point.
4, alkali metallic sodium is dispersed on silica gel, then to react with the tetrahydrofuran of borine at 150 DEG C.Divide at this temperature
Sodium is dissipated, operation is very inconvenient, and with the presence of very high risk.
5, under conditions of ball milling, alkali metallic sodium is dispersed on inorganic salts, such as NaCl, CaCl2Deng equally existing above-mentioned side
Disadvantage in method 4.
In view of the above synthesis M (B3H8)nThe unfavorable factor of class hydroboron, it is necessary to which designing a kind of synthesis process can
The hazardous chemical high using toxicity such as mercury, diboranes is avoided, and easy to operate, safe and reliable boron hydride ion sylvite KB3H8
Synthetic method.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of easy to operate, safe and reliable and less toxic harmless boron hydrogen yin from
Sub- sylvite KB3H8Synthetic method.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, 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, the tetrahydro of borine is then added
Tetrahydrofuran solution is stirred to react obtained target product boron hydride ion sylvite KB in 0~50 DEG C3H8。
Further preferably, the boron hydride ion sylvite KB3H8Synthetic method specific steps are as follows: in nitrogen glove
In case, metallic potassium is fitted into schlenk reaction flask, with after plug seal by schlenk reaction flask remove glove box, then plus
Enter tetrahydrofuran solution (the THF BH for the borine that molar concentration is 0.5~5mol/L3), wherein metallic potassium and THF BH3Feed intake
Molar ratio be 1:2 ~ 1:4, be stirred to react in 0~50 DEG C until metallic potassium completely disappear, be filtered to remove insoluble matter, filtrate be concentrated
It removes solvent and obtains white sticky solid, again with toluene is washed for several times, and then it is pure to obtain white for vacuum concentration removing solvent
Boron hydride ion sylvite KB3H8Powder.
Boron hydride ion sylvite KB of the present invention3H8Synthetic method in reaction equation are as follows:
2K + 4THF•BH3 = KB3H8 + KBH4 + 4THF。
Further preferably, the reaction temperature of synthesis process is preferably room temperature.
Compared with the prior art, the invention has the following beneficial effects: the present invention does not use any medium to disperse alkali gold
Belong to, directly reacted with metallic potassium block, more easy to operate than method before, low toxicity is harmless, securely and reliably, is suitble to scale
Production.
Detailed description of the invention
Fig. 1 is the boron hydride ion sylvite KB that the embodiment of the present invention 1 synthesizes3H8In tetrahydrofuran11B and11B { H } liquid
Body nuclear-magnetism figure, target product obtained is pure KB as seen from the figure3H8。
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment 1
All operations carry out in a nitrogen atmosphere.Schlenk reaction in glove box, to the 100mL equipped with magneton
0.78g metallic potassium is added in bottle, schlenk reaction flask is removed into glove box with after plug seal.Then molar concentration, which is added, is
Tetrahydrofuran solution (the THF BH of the borine of 1mol/L3) 40mL, reaction 8 hours is stirred at room temperature.Insoluble matter is filtered to remove,
Removing solvent is concentrated in filtrate and obtains white sticky solid, again with toluene is washed solid 3 times, then each 20mL is concentrated in vacuo
It removes solvent and obtains white solid product, the pure KB of as solvent-free adduction3H8.Obtained KB3H8It is weighed as 0.64g, is counted
Calculating yield is 80%, and nuclear-magnetism detects its purity close to 100%.
Embodiment 2
All operations carry out in a nitrogen atmosphere.Schlenk reaction in glove box, to the 100mL equipped with magneton
0.78g metallic potassium is added in bottle, schlenk reaction flask is removed into glove box with after plug seal.Then molar concentration, which is added, is
Tetrahydrofuran solution (the THF BH of the borine of 1mol/L3) 80mL, it is stirred to react at 0 DEG C 12 hours.It is filtered to remove insoluble matter, it will
Filtrate concentration removes solvent and obtains white sticky solid, and again with toluene is washed solid 3 times, each 20mL, and then vacuum concentration is removed
Solvent is gone to obtain white solid product, the pure KB of as solvent-free adduction3H8.Obtained KB3H8It is weighed as 0.68g, is calculated
Yield is 85%, and nuclear-magnetism detects its purity close to 100%.
Embodiment 3
All operations carry out in a nitrogen atmosphere.Schlenk reaction in glove box, to the 100mL equipped with magneton
0.78g metallic potassium is added in bottle, schlenk reaction flask is removed into glove box with after plug seal.Then molar concentration, which is added, is
Tetrahydrofuran solution (the THF BH of the borine of 0.5mol/L3) 80mL, reaction 10 hours is stirred at room temperature.It is filtered to remove insoluble
Filtrate is concentrated removing solvent and obtains white sticky solid by object, and again with toluene is washed solid 3 times, and each 20mL, then vacuum is dense
Contracting removes solvent and obtains white solid product, the pure KB of as solvent-free adduction3H8.Obtained KB3H80.68g is weighed as,
Calculating yield is 85%, and nuclear-magnetism detects its purity close to 100%.
Embodiment 4
All operations carry out in a nitrogen atmosphere.Schlenk reaction in glove box, to the 100mL equipped with magneton
0.78g metallic potassium is added in bottle, schlenk reaction flask is removed into glove box with after plug seal.Then molar concentration, which is added, is
Tetrahydrofuran solution (the THF BH of the borine of 5mol/L3) 8mL, it is stirred to react at 50 DEG C 6 hours.It is filtered to remove insoluble matter, it will
Filtrate concentration removes solvent and obtains white sticky solid, and again with toluene is washed solid 3 times, each 20mL, and then vacuum concentration is removed
Solvent is gone to obtain white solid product, the pure KB of as solvent-free adduction3H8.Obtained KB3H8It is weighed as 0.64g, is calculated
Yield is 80%, and nuclear-magnetism detects its purity close to 100%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen 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, the tetrahydrofuran solution THF BH of borine is then added3, obtained target is stirred to react in 0~50 DEG C
Product boron hydride ion sylvite KB3H8。
2. boron hydride ion sylvite KB according to claim 13H8Synthetic method, it is characterised in that specific steps are as follows:
In nitrogen glove box, metallic potassium is fitted into schlenk reaction flask, schlenk reaction flask is removed into gloves with after plug seal
Then the tetrahydrofuran solution THF BH for the borine that molar concentration is 0.5~5mol/L is added in case3, wherein metallic potassium and THF
BH3Molar ratio be 1:2 ~ 1:4, be stirred to react in 0~50 DEG C until metallic potassium completely disappear, be filtered to remove insoluble matter,
Removing solvent is concentrated in filtrate 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 or 23H8Synthetic method, it is characterised in that: synthesis process
Reaction temperature be room temperature.
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| CN107098357B (en) * | 2017-06-10 | 2020-10-30 | 复旦大学 | Preparation method of octahydro-triboric acid compound |
| CN107473184B (en) * | 2017-08-02 | 2019-09-13 | 河南师范大学 | A kind of hydroboron LiB of lithium3H8Synthetic method |
| CN108358165B (en) * | 2018-03-10 | 2021-07-20 | 河南师范大学 | Sodium borohydride salt NaB3H8Preparation method of (1) |
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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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》.1991,第30卷(第14期),第2952-2954页. |
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