| Revision as of 16:24, 9 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 469831220 of page Ammonia_borane for the Chem/Drugbox validation project (updated: 'ChemSpiderID', 'StdInChI', 'StdInChIKey', 'CASNo'). |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{Chembox |
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{{Chembox |
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| Verifiedfields = changed |
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| verifiedrevid = 399507923 |
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| verifiedrevid = 470456677 |
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| ImageFile = Ammonia-borane-from-xtal-3D-balls.png |
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| ImageFile = Ammonia-borane-from-xtal-3D-balls.png |
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| ImageFile_Ref = {{chemboximage|correct|??}} |
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| ImageFile_Ref = {{chemboximage|correct|??}} |
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| ImageSize = 121 |
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| ImageSize = 250 |
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| ImageName = Ball and stick model of ammonia borane |
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| ImageName = Ball and stick model of ammonia borane |
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| IUPACName = Ammonia borane |
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| ImageFile1 = Ammonia borane.png |
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| IUPACName = Ammoniotrihydroborate |
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| OtherNames = Borazane |
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| OtherNames = Borazane<ref name=patents.google>{{cite web | url=https://patents.google.com/patent/WO2015177483A1/en | title=Method for producing borazane }}</ref><ref name=sciencedirect>{{cite journal |last1=Umemoto |first1=Hironobu |last2=Miyata |first2=Atsushi |date=2015 |title=Decomposition processes of diborane and borazane (ammonia-borane complex) on hot wire surfaces |journal=Thin Solid Films |series=8th International conference on hot-wire CVD (Cat-CVD) processes (HWCVD 8) |volume=595 |pages=231–234 |doi=10.1016/j.tsf.2015.04.084|bibcode=2015TSF...595..231U |hdl=10297/10128 |hdl-access=free }}</ref><ref name=sigmaaldrich>{{cite web|title=Results for Borazane|website=sigmaaldrich.com|url=https://www.sigmaaldrich.com/GB/en/search/borazane?focus=products&page=1&perpage=30&sort=relevance&term=borazane&type=product|access-date=2024-09-06}}</ref> |
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| Section1 = {{Chembox Identifiers |
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| Section1 = {{Chembox Identifiers |
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| CASNo_Ref = {{cascite|correct|??}} |
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| CASNo = <!-- blanked - oldvalue: 13774-81-7 --> |
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| CASNo = 13774-81-7 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| PubChem = 419330 |
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| PubChem_Ref = {{Pubchemcite|correct|pubchem}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = XR7O5A5MH6 |
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| ChemSpiderID = 371215 |
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| PubChem = 419330 |
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| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| ChemSpiderID = 371215 |
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| SMILES = |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| SMILES1 = |
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| EINECS = 642-983-4 |
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| StdInChI = 1S/BH3.H3N/h2*1H3 |
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| SMILES = |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChI = 1S/BH6N/c1-2/h1-2H3 |
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| StdInChIKey = WZMUUWMLOCZETI-UHFFFAOYSA-N |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|changed|chemspider}} |
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| StdInChIKey = PJYXJGDRFASJSB-UHFFFAOYSA-N |
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| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| Formula = {{Chem2|H3NBH3}} |
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| H = 6 |
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| B = 1 |
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| B=1|N=1|H=6 |
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| Appearance = Colorless crystals |
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| N = 1 |
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| ExactMass = 31.059329663 g mol<sup>-1</sup> |
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| Density = 0.78 g/cm<sup>3</sup> |
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| MeltingPtC = 104 |
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| Appearance = Colorless solid |
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| Density = 0.780 g cm<sup>-3</sup> |
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| MeltingPtC = 104 |
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| Section3 = {{Chembox Structure |
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| Section3 = {{Chembox Structure |
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| CrystalStruct = I4mm (orthorhombic, < 200K)(tetragonal, >200K) |
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| CrystalStruct = I4mm, tetragonal |
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| Coordination = Tetragonal at B and N |
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| Coordination = Tetragonal at B and N |
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| MolShape = Tetrahydral at B and N |
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| MolShape = Tetrahedral at B and N |
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| Dipole = 5.2 D |
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| Dipole = 5.2 D |
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}} |
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| Section4 = {{Chembox Hazards |
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| Section4 = {{Chembox Hazards |
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| Hazards_ref = <ref name=pubchem>{{cite web | url=https://pubchem.ncbi.nlm.nih.gov/compound/Ammonia-borane | title=Ammonia borane }}</ref> |
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| RPhrases = {{R5}} |
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| SPhrases = {{S14}}, {{S15}}, {{S26}}, {{S36/37/39}} |
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| GHSPictograms = {{GHS02}}{{GHS07}} |
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| GHSSignalWord = Danger |
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| HPhrases = {{H-phrases|H228|H302|H315|H319|H332|H335}} |
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| PPhrases = {{P-phrases|P210|P240|P241|P261|P264|P264+P265|P270|P271|P280|P301+P317|P302+P352|P304+P340|P305+P351+P338|P317|P319|P321|P330|P332+P317|P337+P317|P362+P364|P370+P378|P403+P233|P405|P501}} |
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| Section8 = {{Chembox Related |
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| Section5 = {{Chembox Related |
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| OtherCpds = ]<br /> |
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| OtherCompounds = {{ubl|]|]|]|]|]}} |
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'''Ammonia borane''' (also systematically named '''ammoniotrihydroborate'''{{cn|date=April 2012}}), also called '''borazane''', is the ] with the formula {{chem2|H3NBH3}}. The colourless or white solid is the simplest molecular ]-]-] compound. It has attracted attention as a source of ] fuel, but is otherwise primarily of academic interest. |
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==Synthesis== |
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Reaction of ] with ] mainly gives the diammoniate salt {{chem2|+−]]}} (diammoniodihydroboronium tetrahydroborate). Ammonia borane is the main product when an ] of borane is employed in place of diborane:<ref name="shore">{{cite journal |author1=Shore, S. G. |author2=Boddeker, K. W. | title = Large Scale Synthesis of H<sub>2</sub>B(NH<sub>3</sub>)<sub>2</sub><sup>+</sup>BH<sub>4</sub><sup>−</sup> and H<sub>3</sub>NBH<sub>3</sub> | journal = Inorganic Chemistry | year = 1964 | volume = 3 | issue = 6 | pages = 914–915 | doi = 10.1021/ic50016a038}}</ref> |
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:{{chem2|BH3(]) + NH3 → BH3NH3 + THF}} |
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It can also be synthesized from ].<ref>{{cite journal |last1=Hu |first1=M.G. |last2=Van Paasschen |first2=J.M. |last3=Geanangel |first3=R.A. |title=New synthetic approaches to ammonia-borane and its deuterated derivatives |journal=Journal of Inorganic and Nuclear Chemistry |date=January 1977 |volume=39 |issue=12 |pages=2147–2150 |doi=10.1016/0022-1902(77)80383-7}}</ref><ref>{{cite journal |last1=Ramachandran |first1=P. Veeraraghavan |last2=Mistry |first2=Hitesh |last3=Kulkarni |first3=Ameya S. |last4=Gagare |first4=Pravin D. |title=Ammonia-mediated, large-scale synthesis of ammonia borane |journal=Dalton Trans. |date=2014 |volume=43 |issue=44 |pages=16580–16583 |doi=10.1039/C4DT02467B|pmid=25274135 }}</ref><ref name=Staub /> |
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==Properties and structure== |
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The molecule adopts a structure similar to that of ], with which it is ]. The B−N distance is 1.58(2) Å. The B−H and N−H distances are 1.15 and 0.96 Å, respectively. Its similarity to ethane is tenuous since ammonia borane is a solid and ethane is a gas: their melting points differing by 284 °C. This difference is consistent with the highly polar nature of ammonia borane. The H atoms attached to boron are ] (negatively charged) and those attached to nitrogen are acidic (positively charged).<ref name="Bowden 2007">{{cite journal | last1=Bowden | first1=Mark E. | last2=Gainsford | first2=Graeme J. | last3=Robinson | first3=Ward T. | title=Room-Temperature Structure of Ammonia Borane | journal=Australian Journal of Chemistry | volume=60 | issue=3 | year=2007 | issn=0004-9425 | doi=10.1071/ch06442 | page=149}}</ref> |
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] |
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The structure of the solid indicates a close association of the N''H'' and the B''H'' centers. The closest H−H distance is 1.990 Å, which can be compared with the H−H bonding distance of 0.74 Å. This interaction is called a ].<ref name="klooster">{{cite journal | last = Klooster | first = W. T. |author2= Koetzle, T. F.|author3= Siegbahn, P. E. M.|author4= Richardson, T. B.|author5= Crabtree, R. H. | title = Study of the N−H···H−B Dihydrogen Bond Including the Crystal Structure of BH<sub>3</sub>NH<sub>3</sub> by Neutron Diffraction | journal = ] | year = 1999 | volume = 121 | issue = 27 | pages = 6337–6343 | doi = 10.1021/ja9825332}}</ref><ref name="boese">{{cite book | last = Boese | first = R. |author2= Niederprüm, N.|author3= Bläser, D. | title = Molecules in Natural Science and Medicine | editor = Maksic, Z. B. |editor2=Eckert-Masic, M. | publisher = Ellis Horwood | location = Chichester, England | year = 1992 | isbn = 978-0135615980}}</ref> The original crystallographic analysis of this compound reversed the assignments of B and N. The updated structure was arrived at with improved data using the technique of ] that allowed the hydrogen atoms to be located with greater precision. |
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] |
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{| class="wikitable" style="margin:1em auto; text-align:center;" |
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|+Comparison of bond lengths in simple boron-nitrogen hydrides |
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! Molecule |
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| '''Ammonia borane'''<ref>{{cite journal | first1 = L. R. | last1 = Thorne | first2 = R. D. | last2 = Suenram | first3 = F. J. | last3 = Lovas | title = Microwave spectrum, torsional barrier, and structure of BH<sub>3</sub>NH<sub>3</sub> | journal = ] | volume = 78 | issue = 1 | year = 1983 | pages = 167–171 | doi = 10.1063/1.444528 | bibcode = 1983JChPh..78..167T}}</ref> |
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| ''']'''<ref>{{cite journal | first1 = Masaaki | last1 = Sugie | first2 = Harutoshi | last2 = Takeo | first3 = Chi | last3 = Matsumura | title = Microwave spectrum and molecular structure of aminoborane, BH<sub>2</sub>NH<sub>2</sub> | journal = ] | volume = 123 | issue = 2 | year = 1987 | pages = 286–292 | doi = 10.1016/0022-2852(87)90279-7 | bibcode = 1987JMoSp.123..286S}}</ref> |
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| ''']'''<ref>{{cite journal | first1 = Yoshiyuki | last1 = Kawashima | title = Detection of HBNH by infrared diode laser spectroscopy | journal = ] | year = 1987 | volume = 87 | issue = 11 | pages = 6331–6333 | doi = 10.1063/1.453462 | bibcode = 1987JChPh..87.6331K}}</ref> |
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! Formula |
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| {{chem2|BNH6}} |
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| {{chem2|BNH4}} |
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| {{chem2|BNH2}} |
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! Class |
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| ] |
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| ] |
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| ] |
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! Analogous hydrocarbon |
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| ] |
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| ] |
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| ] |
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! Analogous hydrocarbon class |
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| ] |
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| ] |
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| ] |
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! Structure |
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| ] |
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| ] |
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| ] |
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! ] |
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| ] |
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| ] |
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! Hybridisation of boron and nitrogen |
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| sp<sup>3</sup> |
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| sp<sup>2</sup> |
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| sp |
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! B-N bond length |
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| '''1.658 Å''' |
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| '''1.391 Å''' |
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| '''1.238 Å''' |
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! Proportion of B-N single bond |
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| 100% |
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| 84% |
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| 75% |
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! Structure determination method |
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| ] |
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| microwave spectroscopy |
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==Uses== |
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{{main|Dehydrogenation of amine-boranes}} |
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Ammonia borane has been suggested as a storage medium for ], e.g. for when the gas is used to fuel motor vehicles. It can be made to release hydrogen on heating, being polymerized first to {{chem2|(NH2BH2)_{''n''}|}}, then to {{chem2|(NHBH)_{''n''}|}},<ref>{{cite journal |author1=Gutowski, M. |author2=Autrey, T. | title = Features: Hydrogen gets onboard | journal = Chemistry World | year = 2006 | volume = 3 | issue = 3 | url = http://www.rsc.org/chemistryworld/Issues/2006/March/HydrogenOnBoard.asp}}</ref> which ultimately decomposes to ] (BN) at temperatures above 1000 °C.<ref>{{cite journal |author1=Frueh, S. |author2=Kellett, R. |author3=Mallery, C. |author4=Molter |author5=T. |author6=Willis, W. S. |author7=King'ondu, C. |author8=Suib, S. L. | title = Pyrolytic Decomposition of Ammonia Borane to Boron Nitride | journal = Inorganic Chemistry | year = 2011 | volume = 50 | issue = 3 | pages = 783–792 | doi = 10.1021/ic101020k |pmid=21182274}}</ref> It is more hydrogen-dense than liquid hydrogen and also able to exist at normal temperatures and pressures.<ref>{{cite journal |author1=Stephens, F. H. |author2=Pons, V. |author3=Baker, R. T. | title = Ammonia–Borane: The Hydrogen Source ''par excellence''? | journal = Dalton Transactions | year = 2007 | volume = 2007 | issue = 25 | pages = 2613–2626 | doi = 10.1039/b703053c |pmid=17576485}}</ref> |
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Ammonia borane finds some use in ] as an air-stable derivative of diborane.<ref name="andrews">{{cite encyclopedia | last1 = Andrews | first1 = Glenn C. | last2 = Neelamkavil | first2 = Santhosh F. | title = Borane–Ammonia | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | editor-first = Leo A. | editor-last = Paquette | year = 2008 | publisher = ] | location = ] | doi = 10.1002/047084289X.rb238.pub2 | isbn = 978-0471936237}}</ref> It can be used as a reducing agent in ] reactions, often in the presence of a ] catalyst.<ref>{{cite journal |last1=Zhao |first1=Wenfeng |last2=Li |first2=Hu |last3=Zhang |first3=Heng |last4=Yang |first4=Song |last5=Riisager |first5=Anders |title=Ammonia borane-enabled hydrogen transfer processes: Insights into catalytic strategies and mechanisms |journal=Green Energy & Environment |date=August 2023 |volume=8 |issue=4 |pages=948–971 |doi=10.1016/j.gee.2022.03.011|doi-access=free|bibcode=2023GrEE....8..948Z }}</ref> |
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==Analogous amine-boranes== |
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Many analogues have been prepared from primary, secondary, and even ]s: |
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* ] ({{chem2|(CH3)3C\sNH2→BH3}}) |
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* Borane ] ({{chem2|(CH3)3N→BH3}}) |
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* Borane isopropylamine ({{chem2|(CH3)2CH\sNH2→BH3}}) |
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The first amine adduct of borane was derived from ]. ] is prepared by the reaction of sodium borohydride with t-butylammonium chloride. Generally adduct are more robust with more basic amines. Variations are also possible for the boron component, although primary and secondary boranes are less common.<ref name=Staub> |
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{{cite journal | doi = 10.1021/cr100088b | pmid = 20672860 | title = Ammonia-Borane and Related Compounds as Dihydrogen Sources | journal = Chemical Reviews | volume = 110 | issue = 7 | pages = 4079–4124 | year = 2010 | last1 = Staubitz | first1 = Anne | last2 = Robertson | first2 = Alasdair P. M. | last3 = Manners | first3 = Ian}}</ref> |
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==See also== |
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* ] (''t''BuNH<sub>2</sub>→BH<sub>3</sub>) |
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* ] ({{chem2|R3P→BH3}}) |
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* ] ({{chem2|(CH3)2S→BH3}}) |
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* ] ({{chem2|THF→BH3}}) |
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==References== |
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{{Reflist}} |
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{{Boron compounds}} |
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