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{{chembox |
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{{chembox |
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| verifiedrevid = 455314453 |
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| verifiedrevid = 455336630 |
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| ImageFile = Diethylzinc structure.svg |
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| ImageFile = Diethylzinc structure.svg |
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| ImageSize = |
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| ImageFile1 = Diethylzinc-3D-balls.png |
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| ImageFile1 = Diethylzinc-3D-balls.png |
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| IUPACName = diethylzinc |
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| IUPACName = diethylzinc |
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| Section1 = {{Chembox Identifiers |
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| OtherNames = |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| Section1 = {{Chembox Identifiers |
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|ChemSpiderID = 10413128 |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|InChI = 1/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;/rC4H10Zn/c1-3-5-4-2/h3-4H2,1-2H3 |
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| ChemSpiderID = 10413128 |
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|InChIKey = HQWPLXHWEZZGKY-GFXTWEBUAS |
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| InChI = 1/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;/rC4H10Zn/c1-3-5-4-2/h3-4H2,1-2H3 |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| InChIKey = HQWPLXHWEZZGKY-GFXTWEBUAS |
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|StdInChI = 1S/2C2H5.Zn/c2*1-2;/h2*1H2,2H3; |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/2C2H5.Zn/c2*1-2;/h2*1H2,2H3; |
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|StdInChIKey = HQWPLXHWEZZGKY-UHFFFAOYSA-N |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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| StdInChIKey = HQWPLXHWEZZGKY-UHFFFAOYSA-N |
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|CASNo = 557-20-0 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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|PubChem = 11185 |
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| CASNo = 557-20-0 |
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|ChEBI_Ref = {{ebicite|correct|EBI}} |
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| PubChem = |
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|ChEBI = 51496 |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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|EC_number = 209-161-3 |
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| ChEBI = 51496 |
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|UNNumber = 1366 |
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| SMILES = CCCC |
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|UNII = S0W5NQH7C6 |
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|SMILES = CCCC |
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}} |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| Formula = (C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>Zn |
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|Formula = (C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>Zn |
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| MolarMass = 123.50 g/mol |
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|MolarMass = 123.50 g/mol |
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|Density = 1.205 g/mL |
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| Appearance = |
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|MeltingPtC = -28 |
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| Density = 1.205 g/mL |
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|BoilingPtC = 117 |
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| MeltingPt = -28 °C |
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|Solubility = Reacts |
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| BoilingPt = 117 °C |
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| Solubility = Reacts violently |
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}} |
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| Section3 = {{Chembox Hazards |
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| EUClass = Flammable ('''F'''); Corrosive ('''C'''); Dangerous for the environment ('''N''') |
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| MainHazards = |
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| FlashPt = |
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| Autoignition = |
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}} |
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| Section3 = {{Chembox Hazards |
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'''Diethylzinc''' (C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>Zn, or DEZn, is a highly ] ] comprised of a zinc center bound to two ]s. This colourless liquid is an important ] in ] and available commercially as a solution in ]s, ], or ]. |
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|MainHazards = Flammable and corrosive liquid, pyrophoric in air, may explode in contact with water. |
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|NFPA-H = 1 |
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|NFPA-F = 4 |
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|NFPA-R = 3 |
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|NFPA-S = W |
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| ExternalSDS = |
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|GHSPictograms = {{GHS02}}{{GHS05}}{{GHS09}} |
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|GHSSignalWord = Danger |
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|HPhrases = {{H-phrases|225|250|260|302+312+332|314|410}} |
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|PPhrases = {{P-phrases|210|222|223|231+232|233|240|241|242|243|260|264|273|280|301+330+331|302+334|303+361+353|304+340|305+351+338|310|321|335+334|363|370+378|391|402+404|403+235|405|422|501}} |
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}}<ref>{{Cite web|url=http://www.newenv.com/resources/nfpa_chemicals|title = New Environment Inc. - NFPA Chemicals}}</ref> |
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}} |
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'''Diethylzinc''' (C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>Zn, or DEZ, is a highly ] and reactive ] consisting of a ] center bound to two ]s. This colourless liquid is an important ] in ]. It is available commercially as a solution in ]s, ], or ], or as a pure liquid. |
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==Synthesis== |
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==Synthesis== |
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] first reported the compound in 1848 from zinc and ], the first organozinc compound discovered.<ref>{{cite journal | title = On the isolation of the organic radicals | author = ] | journal = Quarterly Journal of the Chemical Society | year = 1850 | volume = 2 | pages = 263–296 | doi = 10.1039/QJ8500200263 | issue = 3| url = https://zenodo.org/record/1861200}}</ref><ref>{{cite journal | author = Dietmar Seyferth | title = Zinc Alkyls, Edward Frankland, and the Beginnings of Main-Group Organometallic Chemistry | journal = ] | year = 2001 | volume = 20 | issue = 14 | pages = 2940–2955 | doi = 10.1021/om010439f| doi-access = }}</ref> He improved the synthesis by using ] as starting material.<ref>{{cite journal | title = On a new reaction for the production of the zinc-compounds of the alkyl-radical | author = E. Frankland, B. F. Duppa | journal = ]| year = 1864 | volume = 17 | pages = 29–36 | doi = 10.1039/JS8641700029| url =https://zenodo.org/record/1767014}}</ref> The contemporary synthesis consists of the reaction of a 1:1 mixture of ethyl iodide and ethyl bromide with a ], a source of reactive zinc.<ref>{{OrgSynth | author = C. R. Noller | title = Diethyl Zinc | collvol = 2 | collvolpages = 184 | year = 1943 | prep = cv2p0184}}</ref> |
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] first reported the compound in 1848 from zinc and ], the first organozinc compound discovered.<ref>{{cite journal |
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| title = On the isolation of the organic radicals |
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| author = ] |
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| journal = Quarterly ] |
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| year = 1850 |
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| volume = 2 |
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| pages = 263 |
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| doi = 10.1039/QJ8500200263 |
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| issue = 3}}</ref> He improved the synthesis by using diethyl mercury as starting material <ref>{{cite journal |
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| title = On a new reaction for the production of the zinc-compounds of the alkyl-radical |
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| author = ], B. F. Duppa |
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| journal = ] |
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| year = 1864 |
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| volume = 17 |
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| pages = 29–36 |
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| doi = 10.1039/JS8641700029}}</ref> The contemporary synthesis consists of the reaction of a 1:1 mixture of ethyl iodide and ethyl bromide with a ], a source of reactive zinc.<ref>{{OrgSynth | author = C. R. Noller | title = Diethyl Zinc | collvol = 2 | collvolpages = 184 | year = 1943 | prep = cv2p0184}}</ref> |
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==Structure== |
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==Structure== |
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The compound crystallizes in a ] body-centered ] of ] symmetry I4<sub>1</sub>md. In the ] diethylzinc shows nearly linear Zn centres. The Zn-C bonds measure 194.8(5) pm, while the C-Zn-C angle is slightly bent with 176.2(4)°.<ref>{{cite journal | author = John Bacsa, Felix Hanke, Sarah Hindley, Rajesh Odedra, George R. Darling, Anthony C. Jones and Alexander Steiner | title = The Solid State Structures of Dimethylzinc and Diethylzinc | journal = ] | year = 2011 | volume = 50 | pages = 0000-0000 | doi = 10.1002/anie.201105099}}</ref> The structure of the ] shows a very similar Zn-C distance (195.0(2) pm).<ref>{{cite journal | author = A. Haaland, J. C. Green, G. S. McGrady, A. J. Downs, E. Gullo, M. J. Lyall, J. Timberlake, A. V. Tutukin, H. V. Volden, K.-A. Østby | title = The length, strength and polarity of metal–carbon bonds: dialkylzinc compounds studied by density functional theory calculations, gas electron diffraction and photoelectron spectroscopy | journal = ] | year = 2003 | pages = 4356-4366 | doi = 10.1039/B306840B}}</ref> |
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The compound crystallizes in a ] body-centered ] of ] symmetry I4<sub>1</sub>md. In the ] diethylzinc shows nearly linear Zn centres. The Zn-C bonds measure 194.8(5) pm, while the C-Zn-C angle is slightly bent with 176.2(4)°.<ref>{{cite journal |author1=John Bacsa |author2=Felix Hanke |author3=Sarah Hindley |author4=Rajesh Odedra |author5=George R. Darling |author6=Anthony C. Jones |author7=Alexander Steiner | title = The Solid State Structures of Dimethylzinc and Diethylzinc | journal = ] | year = 2011 | volume = 50 |issue=49 | pages = 11685–11687 | doi = 10.1002/anie.201105099|pmc=3326375 | pmid=21919175}}</ref> The structure of the ] shows a very similar Zn-C distance (195.0(2) pm).<ref>{{cite journal |author1=A. Haaland |author2=J. C. Green |author3=G. S. McGrady |author4=A. J. Downs |author5=E. Gullo |author6=M. J. Lyall |author7=J. Timberlake | title = The length, strength and polarity of metal–carbon bonds: dialkylzinc compounds studied by density functional theory calculations, gas electron diffraction and photoelectron spectroscopy | journal = ] |issue=22 | year = 2003 | pages = 4356–4366 | doi = 10.1039/B306840B}}</ref> |
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==Uses== |
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==Uses== |
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Despite its highly pyrophoric nature, diethylzinc is an important chemical reagent. It is used in ] as a source of the ethyl ] in ]s to ] groups. For example, the ] addition of an ] to ]<ref>{{OrgSynth | author = Masato Kitamura, Hiromasa Oka, Seiji Suga, and ] | title = <nowiki>Catalytic Enantioselective Addition of Dialkylzincs to Aldehydes Using (2S)-(−)-3-exo-(Dimethylamino)isoborneol : (S)-1-Phenyl-1-propanol</nowiki> | collvol = 10 | collvolpages = 635 | year = 2004 | prep = v79p0139}}</ref> and ]s.<ref>{{OrgSynth | author = Jean-Nicolas Desrosiers, Alexandre Côté, Alessandro A. Boezio, and André B. Charette | title = Preparation of Enantiomerically Enriched (1S)-1-Phenylpropan-1-amine Hydrochloride by a Catalytic Addition of Diorganozinc Reagents to Imines | volume = 83 | pages = 5 | year = 2005 | prep = v83p0005}}</ref> |
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Despite its highly pyrophoric nature, diethylzinc is an important chemical reagent. It is used in ] as a source of the ethyl ] in ]s to ] groups. For example, the ] addition of an ] to ]<ref>{{OrgSynth | author = Masato Kitamura, Hiromasa Oka, Seiji Suga, and ] | title = <nowiki>Catalytic Enantioselective Addition of Dialkylzincs to Aldehydes Using (2S)-(−)-3-exo-(Dimethylamino)isoborneol : (S)-1-Phenyl-1-propanol</nowiki>| collvol = 10 | collvolpages = 635 | year = 2004 | prep = v79p0139}}</ref> and ]s.<ref>{{OrgSynth | author = Jean-Nicolas Desrosiers, Alexandre Côté, Alessandro A. Boezio, and André B. Charette | title = Preparation of Enantiomerically Enriched (1S)-1-Phenylpropan-1-amine Hydrochloride by a Catalytic Addition of Diorganozinc Reagents to Imines | volume = 83 | pages = 5 | year = 2005 | prep = v83p0005}}</ref> |
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Additionally, it is commonly used in combination with ] as a ] to convert ] into ] groups.<ref>{{OrgSynth | author = André B. Charette and Hélène Lebel | title = (2S,3S)-(+)-(3-Phenylcyclopropyl)methanol | collvol = 10 | collvolpages = 613 | year = 2004 | prep = v76p0086}}</ref><ref>{{OrgSynth | author = Yoshihiko Ito, Shotaro Fujii, Masashi Nakatuska, Fumio Kawamoto, and Takeo Saegusa | title = One-Carbon Ring Expansion of Cycloalkanones to Conjugated Cycloalkenones: 2-Cyclohepten-1-one | collvol = 6 | collvolpages = 327 | year = 1988 | prep = cv6p0327}}</ref>. It is less ] than related ] and ]s, so it may be used when a "softer" nucleophile is needed. |
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Additionally, it is commonly used in combination with ] as a ] to convert ] into ] groups.<ref>{{OrgSynth | author = André B. Charette and Hélène Lebel | title = (2S,3S)-(+)-(3-Phenylcyclopropyl)methanol | collvol = 10 | collvolpages = 613 | year = 2004 | prep = v76p0086}}</ref><ref>{{OrgSynth | author = Yoshihiko Ito, Shotaro Fujii, Masashi Nakatuska, Fumio Kawamoto, and Takeo Saegusa | title = One-Carbon Ring Expansion of Cycloalkanones to Conjugated Cycloalkenones: 2-Cyclohepten-1-one | collvol = 6 | collvolpages = 327 | year = 1988 | prep = cv6p0327}}</ref> It is less ] than related ] and ]s, so it may be used when a "softer" nucleophile is needed. |
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It is also used extensively in ] as a ] source in the synthesis of ]. Particularly in the formation of the ] shell for core/shell-type ].<ref>{{cite journal |
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It is also used extensively in ] chemistry as a zinc source in the synthesis of ]. Particularly in the formation of the ] shell for core/shell-type ].<ref>{{cite journal | title = CdSe/CdS/ZnS and CdSe/ZnSe/ZnS Core−Shell−Shell Nanocrystals |author1=Dmitri V. Talapin |author2=Ivo Mekis |author3=Stephan Götzinger |author4=Andreas Kornowski |author5=Oliver Benson |author6=Horst Weller† | journal = ] | year = 2004 | volume = 108 | pages = 18826–18831 | doi = 10.1021/jp046481g | issue = 49}}</ref> |
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| title = CdSe/CdS/ZnS and CdSe/ZnSe/ZnS Core−Shell−Shell Nanocrystals |
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| author = Dmitri V. Talapin, Ivo Mekis, Stephan Götzinger, Andreas Kornowski, Oliver Benson, and Horst Weller† |
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| journal = ] |
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| year = 2004 |
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| volume = 108 |
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| pages = 18826-18831 |
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| doi = 10.1021/jp046481g |
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| issue = 49}}</ref> |
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While in ], it can be used as part of the catalyst for a ] reaction, whereby it participates in living polymerization.<ref>{{cite journal |
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While in ], it can be used as part of the catalyst for a ] reaction, whereby it participates in living polymerization.<ref>{{cite journal |
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| title = Hydrogen iodide/zinc iodide: a new initiating system for living cationic polymerization of vinyl ethers at room temperature |
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| title = Hydrogen iodide/zinc iodide: a new initiating system for living cationic polymerization of vinyl ethers at room temperature |
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| author = Mitsuo Sawamoto, Chihiro Okamoto, Toshinobu Higashimura |
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|author1=Mitsuo Sawamoto |author2=Chihiro Okamoto |author3=Toshinobu Higashimura |journal = ] | year = 1987 | volume = 20 | pages = 2693–2697 | doi = 10.1021/ma00177a010 | issue = 11|bibcode=1987MaMol..20.2693S }}</ref> |
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| journal = ] |
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| year = 1987 |
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| volume = 20 |
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| pages = 2693-2697 |
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| doi = 10.1021/ma00177a010 |
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| issue = 11}}</ref> |
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Diethyl zinc is not limited to only being used in chemistry. Because of its high reactivity toward air, it was used in small quantities as a ] or "self igniting" liquid rocket fuel -- it ignites on contact with oxidiser, so the rocket motor need only contain a pump, without a spark source for ignition. Diethylzinc was also investigated by the United States ] as a potential means of ] of books printed on wood pulp paper. Vapor of diethylzinc vapour would in theory, neutralize acid residues in the paper, leaving slightly ]ne ] residues. Although initial results were promising, the project was abandoned. A variety of adverse results prevented the methods adoption. Most infamously, the final prototype suffered damage in a series of explosions from contact between trace amounts of diethylzinc and water vapor in the chamber. This lead the authors of the study to humorously comment:<ref>{{Citation |
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Diethylzinc is not limited to only being used in chemistry. Because of its high reactivity toward air, it was used in small quantities as a ] or "self igniting" liquid rocket fuel<ref name=Clark2018>{{cite book |isbn = 978-0-8135-9918-2 |title = Ignition!: An Informal History of Liquid Rocket Propellants |last1 = Clark |first1 = John Drury |author-link=John Drury Clark |date = 23 May 2018 |publisher = Rutgers University Press |url=https://books.google.com/books?id=BdU4DwAAQBAJ&q=diethyl%20zinc |pages=302 |oclc=281664}}</ref>{{rp|9}}<ref name="Sutton">{{Cite book | last1 = Sutton | first1 = George P. | last2 = Biblarz | first2 = Oscar | title = Rocket Propulsion Elements - Seventh Edition | publisher = John Wiley & Sons, Inc. | year = 2001 | isbn = 0-471-32642-9 |url = http://mae-nas.eng.usu.edu/MAE_5540_Web/propulsion_systems/subpages/Rocket_Propulsion_Elements.pdf | url-status=live | archive-url=https://web.archive.org/web/20220228001253/http://mae-nas.eng.usu.edu/MAE_5540_Web/propulsion_systems/subpages/Rocket_Propulsion_Elements.pdf |archive-date=28 February 2022}}</ref>{{rp|323}}—it ignites on contact with oxidizer, so the rocket motor need only contain a pump, without a spark source for ignition. Diethylzinc was also investigated by the United States ] as a potential means of ] of books printed on wood pulp paper. Diethylzinc vapour would, in theory, neutralize acid residues in the paper, leaving slightly ]ne ] residues. Although initial results were promising, the project was abandoned. A variety of adverse results prevented the method's adoption. Most infamously, the final prototype suffered damage in a series of diethylzinc explosions from trace amounts of water vapor in the chamber. This led the authors of the study to humorously comment:{{blockquote| It has also been established that tight or loose packing of books; the amount of alkaline reserve; reactions of DEZ with degradation products, unknown paper chemicals and adhesives; phases of the moon and the positions of various planets and constellations do not have any influence on the observed adverse effects of DEZ treatment.<ref>{{Citation |author1 = Kenneth E. Harris|author2 = Chandru J. Shahani |year = 2004 |title = Mass Deacidification: An Initiative To Refine The Diethyl Zinc Process |publisher = ] |location = ] |url = https://www.loc.gov/preservation/resources/deacid/dez.pdf |url-status = dead|archiveurl =https://web.archive.org/web/20130514014013/http://www.loc.gov/preservation/resources/deacid/dez.pdf|archivedate = 2013-05-14}}</ref>}} |
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In microelectronics, diethylzinc is used as a ].{{Citation needed|date=December 2007}} |
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|author= Kenneth E. Harris and Chandru J. Shahani |
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|year= 2004 |
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For corrosion protection in ] of the ] design, ] is produced by first passing diethylzinc through an ] centrifuge. |
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|title= Mass Deacidification: An Initiative To Refine The Diethyl Zinc Process |
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|publisher= ] |
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The pyrophoricity of diethylzinc can be used to test the inert atmosphere inside a ]. An oxygen concentration of only a few parts per million will cause a bottle of diethylzinc to fume when opened.<ref>{{Cite book|last1=Shriver|first1=Duward F.|title=The Manipulation of Air-Sensitive Compounds|last2=Drezdzon|first2=Mark A.|publisher=John Wiley & Sons|year=1986|isbn=0-471-86773-X|pages=57}}</ref> |
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|publication-place= ] |
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|url= http://www.loc.gov/preservation/resources/deacid/dez.pdf |
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}}</ref> {{quotation | It has also been established that tight or loose packing of books; the amount of alkaline reserve; reactions of DEZ with degradation products, unknown paper chemicals and adhesives; phases of the moon and the positions of various planets and constellations do not have any influence on the observed adverse effects of DEZ treatment.}} |
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In microelectronics, diethylzinc is used as a ].{{Fact|date=December 2007}} |
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==Safety== |
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==Safety== |
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Diethylzinc reacts violently with water and easily ] upon contact with air. It should therefore be handled using ]s. |
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Diethylzinc may explode when mixed with water and can spontaneously ]. It should therefore be handled using ]s. |
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==References== |
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==References== |
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==External links== |
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==External links== |
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* Demonstration of the ignition of Diethylzinc in air |
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*Demonstration of the ignition of diethylzinc in air |
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{{Zinc compounds}} |
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* Diethylzinc, 15 wt.% solution in hexane |
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* Diethylzinc purum |
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* Diethylzinc |
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* Diethylzinc |
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