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Revision as of 12:37, 10 January 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,081 edits Saving copy of the {{chembox}} taken from revid 456682121 of page Tetrahedrane for the Chem/Drugbox validation project (updated: '').		Latest revision as of 20:05, 21 July 2024 edit LaundryPizza03 (talk | contribs)Extended confirmed users54,395 edits added Category:Tetrahedra using HotCat
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			{{Short description|Hypothetical organic molecule with a tetrahedral structure}}
	{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}}
	{{Chembox		{{Chembox
			| Watchedfields = changed
	| verifiedrevid = 397778641		| verifiedrevid = 470603989
	| ImageFile = Tetrahedrane-3D-balls.png		| ImageFile = Tetrahedrane-3D-balls.png
	| ImageSize = 244		| ImageSize =
	| ImageName = Ball and stick model of tetrahedrane		| ImageName = Ball and stick model of tetrahedrane
		⚫	| PIN = Tricyclobutane
	| PIN = Tetrahedrane
⚫	| SystematicName = Tricyclobutane
	| Section1 = {{Chembox Identifiers		| Section1 = {{Chembox Identifiers
	| PubChem = 9548696		| PubChem = 9548696
		⚫	| ChemSpiderID = 7827619
	| PubChem_Ref = {{Pubchemcite|correct|PubChem}}
		⚫	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
⚫	| ChemSpiderID = 7827619
			| CASNo = 157-39-1
⚫	| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
	| ChEBI_Ref = {{ebicite|correct|EBI}}		| ChEBI_Ref = {{ebicite|correct|EBI}}
	| ChEBI = 36549		| ChEBI = 36549
	| SMILES = C12C3C1C23		| SMILES = C12C3C1C23
	| StdInChI_Ref = {{stdinchicite|correct|chemspider}}		| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChI = 1S/C4H4/c1-2-3(1)4(1)2/h1-4H		| StdInChI = 1S/C4H4/c1-2-3(1)4(1)2/h1-4H
	| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}		| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
	| StdInChIKey = FJGIHZCEZAZPSP-UHFFFAOYSA-N		| StdInChIKey = FJGIHZCEZAZPSP-UHFFFAOYSA-N
	| Beilstein = 2035811}}		| Beilstein = 2035811}}
	| Section2 = {{Chembox Properties		| Section2 = {{Chembox Properties
	| C = 4		| C = 4
	| H = 4		| H = 4
	| ExactMass = 52.031300128 g mol<sup>-1</sup>}}
	}}		}}
			}}
			'''Tetrahedrane''' is a hypothetical ] with ] {{chem2|C4H4}} and a ] structure. The molecule would be subject to considerable ] and has not been synthesized {{as of|2023|lc=y}}. However, a number of ] have been prepared. In a more general sense, the term ''tetrahedranes'' is used to describe a class of molecules and ]s with related structure, e.g. ].
			==Organic tetrahedranes==
			In 1978, Günther Maier prepared tetra-''tert''-butyl-tetrahedrane.<ref>{{cite journal | first1= G.|last1= Maier|first2=S. |last2=Pfriem|first3= U. |last3=Schäfer |first4=R.|last4= Matusch | title = Tetra-''tert''-butyltetrahedrane | year = 1978 | journal = ] | volume = 17 |issue= 7| pages = 520–521 | doi = 10.1002/anie.197805201}}</ref> The bulky ] (''t''-Bu) substituents envelop the tetrahedrane core. Maier suggested that bonds in the core are prevented from breaking because this would force the substituents closer together ('''corset effect''') resulting in ]. Tetrahedrane is one of the possible ] and has the ] tricyclobutane.
			Unsubstituted tetrahedrane ({{chem2|C4H4}}) remains elusive, although it is predicted to be kinetically stable. One strategy that has been explored (but thus far failed) is reaction of ] with ].<ref>{{cite journal|title=Tetrahedrane—Dossier of an Unknown|first1=Adelina|last1=Nemirowski|first2=Hans Peter|last2=Reisenauer|first3=Peter R.|last3=Schreiner|journal=Chem. Eur. J.|date=2006|volume=12|issue=28|pages=7411–7420|doi=10.1002/chem.200600451|pmid=16933255}}</ref> Locking away a tetrahedrane molecule inside a ] has only been attempted '']''.<ref>{{cite journal|title=Endohedral complex of fullerene C<sub>60</sub> with tetrahedrane, C<sub>4</sub>H<sub>4</sub>@C<sub>60</sub>|first1=Xiao-Yuan|last1=Ren|first2=Cai-Ying|last2=Jiang|first3=Jiang|last3=Wang|first4=Zi-Yang|last4=Liu|journal=J. Mol. Graph. Model.|volume=27|issue=4|date=2008|pages=558–562|doi=10.1016/j.jmgm.2008.09.010|pmid=18993098}}</ref> Due to its bond strain and stoichiometry, tetranitrotetrahedrane has potential as a high-performance energetic material (explosive).<ref>{{cite journal | doi=10.1016/j.theochem.2003.10.054 | volume=668 | issue=2–3 | title=Computational studies on a kind of novel energetic materials tetrahedrane and nitro derivatives | journal=Journal of Molecular Structure: Theochem | pages=189–195| year=2004 | last1=Zhou | first1=Ge | last2=Zhang | first2=Jing-Lai | last3=Wong | first3=Ning-Bew | last4=Tian | first4=Anmin }}</ref> Some properties have been calculated based on ].<ref>{{cite journal | first1= Peter D.|last1= Jarowski|first2= Francois |last2=Diederich|first3= Kendall N. |last3=Houk | title = Structures and Stabilities of Diacetylene-Expanded Polyhedranes by Quantum Mechanics and Molecular Mechanics | year = 2005 | journal = ] | volume = 70 |issue= 5| pages = 1671–1678 | doi = 10.1021/jo0479819|pmid= 15730286}}</ref>
			===Tetra-''tert''-butyltetrahedrane===
			This compound was first synthesised starting from a ] of an ] with ''t''-Bu substituted ],<ref>{{cite journal | doi = 10.1016/S0040-4039(01)84500-7 | title = ''tert''-Butyl-substituierte cyclobutadiene und cyclopentadienone | trans-title = ''tert''-Butyl-substituted cyclobutadienes and cyclopentadienones | year = 1972 | last1 = Maier | first1 = Günther | last2 = Boßlet | first2 = Friedrich | journal = Tetrahedron Letters | volume = 13 | issue = 11 | pages = 1025–1030}}</ref> followed by rearrangement with carbon dioxide expulsion to a ] and its ], followed by addition of the fourth ''t''-Bu group. Photochemical ] of ] of the cyclopentadienone gives the target. Heating tetra-''tert''-butyltetrahedrane gives tetra-''tert''-butyl]. Though the synthesis appears short and simple, by Maier's own account, it took several years of careful observation and optimization to develop the correct conditions for the challenging reactions to take place. For instance, the synthesis of tetrakis(''t-''butyl)cyclopentadienone from the tris(''t''-butyl)bromocyclopentadienone (itself synthesized with much difficulty) required over 50 attempts before working conditions could be found.<ref>{{Cite journal|last1=Maier|first1=Günther|last2=Pfriem|first2=Stephan|last3=Schäfer|first3=Ulrich|last4=Malsch|first4=Klaus-Dieter|last5=Matusch|first5=Rudolf|date=December 1981|title=Kleine Ringe, 38: Tetra-tert-butyltetrahedran|journal=Chemische Berichte|language=de|volume=114|issue=12|pages=3965–3987|doi=10.1002/cber.19811141218}}</ref> The synthesis was described as requiring "astonishing persistence and experimental skill" in one retrospective of the work.<ref>{{Cite book|title=Modeling marvels : computational anticipation of novel molecules|last=Lewars, Errol.|date=2008|publisher=Springer|isbn=978-1-4020-6973-4|location=|oclc=314371890}}</ref> In a classic reference work on stereochemistry, the authors remark that "the relatively straightforward scheme shown conceals both the limited availability of the starting material and the enormous amount of work required in establishing the proper conditions for each step."<ref>{{Cite book|title=Stereochemistry of organic compounds|last=Eliel, Ernest L. (Ernest Ludwig), 1921-2008.|date=1994|publisher=Wiley|others=Wilen, Samuel H., Mander, Lewis N.|isbn=0-471-01670-5|location=New York|oclc=27642721}}</ref>
			:]
			Eventually, a more scalable synthesis was conceived, in which the last step was the photolysis of a cyclopropenyl-substituted diazomethane, which affords the desired product through the intermediacy of tetrakis(''tert''-butyl)cyclobutadiene:<ref>{{Cite journal|last1=Maier|first1=Günther|last2=Fleischer|first2=Frank|date=1991-01-01|title=Ein alternativer zugang zum tetra-tert-butyltetrahedran|journal=Tetrahedron Letters|language=de|volume=32|issue=1|pages=57–60|doi=10.1016/S0040-4039(00)71217-2|issn=0040-4039}}</ref><ref>{{Cite journal|title=Recent Advances in Cyclopropene Chemistry|last1=Rubin|first1=M.|last2=Rubina|first2=M.|journal=Synthesis|doi=10.1055/s-2006-926404|last3=Gevorgyan|first3=V.|year=2006|volume=2006|issue=8|pages=1221–1245}}</ref> This approach took advantage of the observation that the tetrahedrane and the cyclobutadiene could be interconverted (uv irradiation in the forward direction, heat in the reverse direction).
			:]
			<br />
			===Tetrakis(trimethylsilyl)tetrahedrane===
			]
			Tetrakis(trimethylsilyl)tetrahedrane can be prepared by treatment of the cyclobutadiene precursor with ]<ref>{{cite journal|last1=Nakamoto|first1=M.|last2=Inagaki|first2=Y.|last3=Ochiai|first3=T.|last4=Tanaka|first4=M.|last5=Sekiguchi|first5=A.|date=2011|title=Cyclobutadiene to tetrahedrane: Valence isomerization induced by one-electron oxidation|journal= Heteroatom Chemistry|volume=22|issue=3–4|pages=412–416|doi=10.1002/hc.20699}}</ref> and is far more stable than the ''tert''-butyl analogue. The silicon–carbon ] is longer than a carbon–carbon bond, and therefore the corset effect is reduced.<ref>{{cite journal|title=Tetrakis(trimethylsilyl)tetrahedrane|first1=Günther|last1=Maier|first2=Jörg|last2=Neudert|first3=Oliver|last3=Wolf|first4=Dirk|last4=Pappusch|first5=Akira|last5=Sekiguchi|first6=Masanobu|last6=Tanaka|first7=Tsukasa|last7=Matsuo|journal=J. Am. Chem. Soc.|date=2002|volume=124|issue=46|pages=13819–13826|doi=10.1021/ja020863n|pmid=12431112}}</ref> Whereas the ''tert''-butyl tetrahedrane melts at 135&nbsp;] concomitant with rearrangement to the cyclobutadiene, tetrakis(trimethylsilyl)tetrahedrane, which melts at 202&nbsp;°C, is stable up to 300&nbsp;°C, at which point it cracks to bis(trimethylsilyl)acetylene.
			The tetrahedrane skeleton is made up of ]s, and hence the carbon atoms are high in ] character. From ], sp-] can be deduced, normally reserved for ]s. As a consequence the ]s are unusually short with 152 ]s.
			Reaction with ] with tetrakis(trimethylsilyl)tetrahedrane yields tetrahedranyllithium.<ref>{{cite journal|title=Tetrahedranyllithium: Synthesis, Characterization, and Reactivity|first1=Akira|last1=Sekiguchi|first2=Masanobu|last2=Tanaka|journal=J. Am. Chem. Soc.|date=2003|volume=125|issue=42|pages=12684–5|doi=10.1021/ja030476t|pmid=14558797}}</ref> ] with this lithium compound gives extended structures.<ref>{{cite journal|title=Perfluoroaryltetrahedranes: Tetrahedranes with Extended σ−π Conjugation|first1=Masaaki|last1=Nakamoto|first2=Yusuke|last2=Inagaki|first3=Motoaki|last3=Nishina|first4=Akira|last4=Sekiguchi|journal=J. Am. Chem. Soc.|date=2009|volume=131|issue=9|pages=3172–3|doi=10.1021/ja810055w|pmid=19226138}}</ref><ref>{{cite journal|title=Sulfur-Substituted Tetrahedranes|first1=Tatsumi|last1=Ochiai|first2=Masaaki|last2=Nakamoto|first3=Yusuke|last3=Inagaki|first4=Akira|last4=Sekiguchi|journal=J. Am. Chem. Soc.|date=2011|volume=133|issue=30|pages=11504–7|doi=10.1021/ja205361a|pmid= 21728313|url=https://figshare.com/articles/Sulfur_Substituted_Tetrahedranes/2626860}}</ref><ref>{{cite journal | last1 = Kobayashi | first1 = Y. | last2 = Nakamoto | first2 = M. | last3 = Inagaki | first3 = Y. | last4 = Sekiguchi | first4 = A. | year = 2013 | title = Cross-Coupling Reaction of a Highly Strained Molecule: Synthesis of σ–π Conjugated Tetrahedranes | journal = Angew. Chem. Int. Ed. | volume = 52 | issue = 41 | pages = 10740–10744 | doi = 10.1002/anie.201304770 | pmid = 24038655 | s2cid = 30151404 }}</ref>
			A bis(tetrahedrane) has also been reported.<ref>{{cite journal | first1= M.|last1= Tanaka |first2= A.|last2= Sekiguchi | title = Hexakis(trimethylsilyl)tetrahedranyltetrahedrane | year = 2005 | journal = ] | volume = 44 | issue = 36 | pages = 5821–5823 | doi = 10.1002/anie.200501605 | pmid = 16041816}}</ref> The connecting bond is even shorter with 143.6&nbsp;pm. An ordinary carbon–carbon bond has a length of 154&nbsp;pm.
			:]
			==Tetrahedranes with non-carbon cores==
			In tetrasilatetrahedrane features a core of four ] atoms. The standard silicon–silicon bond is much longer (235&nbsp;pm) and the cage is again enveloped by a total of 16 ] groups, which confer stability. The silatetrahedrane can be ] with ] to the tetrasilatetrahedranide potassium derivative. In this compound one of the silicon atoms of the cage has lost a silyl substituent and carries a negative charge. The potassium cation can be sequestered by a ], and in the resulting complex potassium and the silyl anion are separated by a distance of 885&nbsp;pm. One of the Si<sup>−</sup>–Si bonds is now 272&nbsp;pm and the tetravalent silicon atom of that bond has an ]. Furthermore, the four cage silicon atoms are equivalent on the ] timescale due to migrations of the silyl substituents over the cage.<ref>{{cite journal | title = Tetrasilatetrahedranide: A Silicon Cage Anion | first1= Masaaki|last1= Ichinohe|first2= Masafumi|last2= Toyoshima|first3= Rei |last3=Kinjo|first4= Akira |last4=Sekiguchi | journal = ] | year = 2003 | volume = 125 | issue = 44 | pages = 13328–13329| doi = 10.1021/ja0305050 | pmid = 14583007}}</ref>
			:]
			The dimerization reaction observed for the carbon tetrahedrane compound is also attempted for a tetrasilatetrahedrane.<ref>{{cite journal | first1= G. | last1=Fischer| first2= V. | last2=Huch| first3= P. | last3=Mayer| first4= S. K. | last4=Vasisht| first5= M. | last5=Veith | first6= N.| last6= Wiberg | title = Si<SUB>8</SUB>(Si''t''Bu<SUB>3</SUB>)<SUB>6</SUB>: A Hitherto Unknown Cluster Structure in Silicon Chemistry | year = 2005 | journal = ] | volume = 44 | issue = 48 | pages = 7884–7887 | doi = 10.1002/anie.200501289 | pmid = 16287188}}</ref> In this tetrahedrane the cage is protected by four so-called ]s in which a silicon atom has 3 ] substituents. The dimer does not materialize but a reaction with ] in benzene followed by reaction with the tri-''tert''-butylsilaanion results in the formation of an eight-membered silicon ] which can be described as a {{chem2|Si2}} dumbbell (length 229&nbsp;pm and with inversion of tetrahedral geometry) sandwiched between two almost-parallel {{chem2|Si3}} rings.
			:]
			In eight-membered clusters of in the same ], ] {{chem2|Sn8R6}} and ] {{chem2|Ge8R6}} the cluster atoms are located on the corners of a cube.
			==Inorganic and organometallic tetrahedranes==
			4}}, a tetrahedrane with an {{chem2|In4}} core (dark gray = In, orange = Si).<ref>{{cite journal|doi=10.1016/0022-328X(95)05399-A|title=In4{C(SiMe<sub>3</sub>)<sub>3</sub>}<sub>4</sub> mit In<sub>4</sub>-tetraeder und In<sub>4</sub>Se<sub>4</sub>{C(SiMe<sub>3</sub>)<sub>3</sub>}<sub>4</sub> mit In<sub>4</sub>Se<sub>4</sub>-heterocubanstruktur|journal=Journal of Organometallic Chemistry|volume=493|issue=1–2|pages=C1–C5|year=1995|last1=Uhl|first1=Werner|last2=Graupner|first2=Rene|last3=Layh|first3=Marcus|last4=Schütz|first4=Uwe}}
			</ref>]]
			]
			The tetrahedrane motif occurs broadly in chemistry. ] (P<sub>4</sub>) and ] (As<sub>4</sub>) are examples. Several metal carbonyl clusters are referred to as tetrahedranes, e.g. ].
			Metallatetrahedranes with a single metal (or phosphorus atom) capping a cyclopropyl trianion also exist.<ref>
			*Organometallics 2019, 38, 21, 4054–4059.
			*Organometallics 1984, 3, 1574−1583.
			*Organometallics 1986, 5, 25−33.
			*J. Am. Chem. Soc. 1984, 106, 3356−3357.
			*J. Chem. Soc., Chem. Commun. 1984, 485−486.
			*Science Advances 25 Mar 2020: Vol. 6, no. 13, ]
			</ref>
			{{clear}}
			==See also==
			*]
			*]
			*]
			*]
			== References ==
			{{reflist|30em}}
			]
			]
			]
			]
			]