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{{chembox {{chembox
| Watchedfields = changed
| verifiedrevid = 455336630
| verifiedrevid = 455336630
| ImageFile = Diethylzinc structure.svg
| ImageFile = Diethylzinc structure.svg
| ImageSize =
| ImageFile1 = Diethylzinc-3D-balls.png | ImageFile1 = Diethylzinc-3D-balls.png
| IUPACName = diethylzinc | IUPACName = diethylzinc
| Section1 = {{Chembox Identifiers
| OtherNames =
|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| Section1 = {{Chembox Identifiers
|ChemSpiderID = 10413128
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
|InChI = 1/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;/rC4H10Zn/c1-3-5-4-2/h3-4H2,1-2H3
| ChemSpiderID = 10413128
|InChIKey = HQWPLXHWEZZGKY-GFXTWEBUAS
| InChI = 1/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;/rC4H10Zn/c1-3-5-4-2/h3-4H2,1-2H3
|StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| InChIKey = HQWPLXHWEZZGKY-GFXTWEBUAS
|StdInChI = 1S/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;
|StdInChIKey = HQWPLXHWEZZGKY-UHFFFAOYSA-N
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
|CASNo_Ref = {{cascite|correct|CAS}}
| StdInChIKey = HQWPLXHWEZZGKY-UHFFFAOYSA-N
|CASNo = 557-20-0
| CASNo_Ref = {{cascite|correct|CAS}}
|PubChem = 11185
| CASNo = 557-20-0
|ChEBI_Ref = {{ebicite|correct|EBI}}
| PubChem =
|ChEBI = 51496
| ChEBI_Ref = {{ebicite|correct|EBI}}
|EC_number = 209-161-3
| ChEBI = 51496
|UNNumber = 1366
| SMILES = CCCC
|UNII = S0W5NQH7C6
|SMILES = CCCC
}} }}
| Section2 = {{Chembox Properties | Section2 = {{Chembox Properties
| Formula = (C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>Zn |Formula = (C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>Zn
| MolarMass = 123.50 g/mol |MolarMass = 123.50 g/mol
|Density = 1.205 g/mL
| Appearance =
|MeltingPtC = -28
| Density = 1.205 g/mL
|BoilingPtC = 117
| MeltingPt = -28 °C
|Solubility = Reacts
| BoilingPt = 117 °C
| Solubility = Reacts violently
}}
| Section3 = {{Chembox Hazards
| EUClass = Flammable ('''F'''); Corrosive ('''C'''); Dangerous for the environment ('''N''')
| MainHazards =
| FlashPt =
| Autoignition =
}}
}} }}
| Section3 = {{Chembox Hazards
'''Diethylzinc''' (C<sub>2</sub>H<sub>5</sub>)<sub>2</sub>Zn, or DEZn, is a highly ] ] consisting of a zinc center bound to two ]s. This colourless liquid is an important ] in ] and available commercially as a solution in ]s, ], or ].
|MainHazards = Flammable and corrosive liquid, pyrophoric in air, may explode in contact with water.
|NFPA-H = 1
|NFPA-F = 4
|NFPA-R = 3
|NFPA-S = W
| ExternalSDS =
|GHSPictograms = {{GHS02}}{{GHS05}}{{GHS09}}
|GHSSignalWord = Danger
|HPhrases = {{H-phrases|225|250|260|302+312+332|314|410}}
|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}}
}}<ref>{{Cite web|url=http://www.newenv.com/resources/nfpa_chemicals|title = New Environment Inc. - NFPA Chemicals}}</ref>
}}
'''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.


==Synthesis== ==Synthesis==
] 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>
] 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 ]
| year = 1850
| volume = 2
| pages = 263
| doi = 10.1039/QJ8500200263
| issue = 3}}</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 | pages = 2940–2955 | doi = 10.1021/om010439f}}</ref> He improved the synthesis by using diethyl mercury as starting material <ref>{{cite journal
| title = On a new reaction for the production of the zinc-compounds of the alkyl-radical
| author = ], B. F. Duppa
| journal = ]
| year = 1864
| volume = 17
| pages = 29–36
| 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>


==Structure== ==Structure==
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> 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>


==Uses== ==Uses==
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> 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>
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. 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.
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 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>
| title = CdSe/CdS/ZnS and CdSe/ZnSe/ZnS Core−Shell−Shell Nanocrystals
| author = Dmitri V. Talapin, Ivo Mekis, Stephan Götzinger, Andreas Kornowski, Oliver Benson, and Horst Weller†
| journal = ]
| year = 2004
| volume = 108
| pages = 18826–18831
| doi = 10.1021/jp046481g
| issue = 49}}</ref>
While in ], it can be used as part of the catalyst for a ] reaction, whereby it participates in living polymerization.<ref>{{cite journal While in ], it can be used as part of the catalyst for a ] reaction, whereby it participates in living polymerization.<ref>{{cite journal
| title = Hydrogen iodide/zinc iodide: a new initiating system for living cationic polymerization of vinyl ethers at room temperature | title = Hydrogen iodide/zinc iodide: a new initiating system for living cationic polymerization of vinyl ethers at room temperature
| author = Mitsuo Sawamoto, Chihiro Okamoto, Toshinobu Higashimura |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>
| journal = ]
| year = 1987
| volume = 20
| pages = 2693–2697
| doi = 10.1021/ma00177a010
| issue = 11}}</ref>


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 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>}}
In microelectronics, diethylzinc is used as a ].{{Citation needed|date=December 2007}}
|author= Kenneth E. Harris and Chandru J. Shahani

|year= 2004
For corrosion protection in ] of the ] design, ] is produced by first passing diethylzinc through an ] centrifuge.
|title= Mass Deacidification: An Initiative To Refine The Diethyl Zinc Process

|publisher= ]
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>
|publication-place= ]
|url= http://www.loc.gov/preservation/resources/deacid/dez.pdf
}}</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.}}
In microelectronics, diethylzinc is used as a ].{{Fact|date=December 2007}}


==Safety== ==Safety==
Diethylzinc reacts violently with water and easily ] upon contact with air. It should therefore be handled using ]s. Diethylzinc may explode when mixed with water and can spontaneously ]. It should therefore be handled using ]s.


==References== ==References==
Line 100: Line 75:


==External links== ==External links==
* Demonstration of the ignition of Diethylzinc in air *Demonstration of the ignition of diethylzinc in air
{{Zinc compounds}}


] ]
] ]
]

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]
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]
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Latest revision as of 22:49, 26 August 2024

Diethylzinc
Names
IUPAC name diethylzinc
Identifiers
CAS Number
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.008.330 Edit this at Wikidata
EC Number
  • 209-161-3
PubChem CID
UNII
UN number 1366
CompTox Dashboard (EPA)
InChI
  • InChI=1S/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;Key: HQWPLXHWEZZGKY-UHFFFAOYSA-N
  • InChI=1/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;/rC4H10Zn/c1-3-5-4-2/h3-4H2,1-2H3Key: HQWPLXHWEZZGKY-GFXTWEBUAS
SMILES
  • CCCC
Properties
Chemical formula (C2H5)2Zn
Molar mass 123.50 g/mol
Density 1.205 g/mL
Melting point −28 °C (−18 °F; 245 K)
Boiling point 117 °C (243 °F; 390 K)
Solubility in water Reacts
Hazards
Occupational safety and health (OHS/OSH):
Main hazards Flammable and corrosive liquid, pyrophoric in air, may explode in contact with water.
GHS labelling:
Pictograms GHS02: FlammableGHS05: CorrosiveGHS09: Environmental hazard
Signal word Danger
Hazard statements H225, H250, H260, H302+H312+H332, H314, H410
Precautionary statements P210, P222, P223, P231+P232, P233, P240, P241, P242, P243, P260, P264, P273, P280, P301+P330+P331, P302+P334, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P335+P334, P363, P370+P378, P391, P402+P404, P403+P235, P405, P422, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 4: Will rapidly or completely vaporize at normal atmospheric pressure and temperature, or is readily dispersed in air and will burn readily. Flash point below 23 °C (73 °F). E.g. propaneInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazard W: Reacts with water in an unusual or dangerous manner. E.g. sodium, sulfuric acid
1 4 3W
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

Diethylzinc (C2H5)2Zn, or DEZ, is a highly pyrophoric and reactive organozinc compound consisting of a zinc center bound to two ethyl groups. This colourless liquid is an important reagent in organic chemistry. It is available commercially as a solution in hexanes, heptane, or toluene, or as a pure liquid.

Synthesis

Edward Frankland first reported the compound in 1848 from zinc and ethyl iodide, the first organozinc compound discovered. He improved the synthesis by using diethyl mercury as starting material. The contemporary synthesis consists of the reaction of a 1:1 mixture of ethyl iodide and ethyl bromide with a zinc-copper couple, a source of reactive zinc.

Structure

The compound crystallizes in a tetragonal body-centered unit cell of space group symmetry I41md. In the solid-state 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)°. The structure of the gas-phase shows a very similar Zn-C distance (195.0(2) pm).

Uses

Despite its highly pyrophoric nature, diethylzinc is an important chemical reagent. It is used in organic synthesis as a source of the ethyl carbanion in addition reactions to carbonyl groups. For example, the asymmetric addition of an ethyl group to benzaldehyde and imines. Additionally, it is commonly used in combination with diiodomethane as a Simmons-Smith reagent to convert alkenes into cyclopropyl groups. It is less nucleophilic than related alkyllithium and Grignard reagents, so it may be used when a "softer" nucleophile is needed. It is also used extensively in materials science chemistry as a zinc source in the synthesis of nanoparticles. Particularly in the formation of the zinc sulfide shell for core/shell-type quantum dots. While in polymer chemistry, it can be used as part of the catalyst for a chain shuttling polymerization reaction, whereby it participates in living polymerization.

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 hypergolic or "self igniting" liquid rocket fuel—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 Library of Congress as a potential means of mass deacidification of books printed on wood pulp paper. Diethylzinc vapour would, in theory, neutralize acid residues in the paper, leaving slightly alkaline zinc oxide 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:

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.

In microelectronics, diethylzinc is used as a doping agent.

For corrosion protection in nuclear reactors of the light water reactor design, depleted zinc oxide is produced by first passing diethylzinc through an enrichment centrifuge.

The pyrophoricity of diethylzinc can be used to test the inert atmosphere inside a glovebox. An oxygen concentration of only a few parts per million will cause a bottle of diethylzinc to fume when opened.

Safety

Diethylzinc may explode when mixed with water and can spontaneously ignite upon contact with air. It should therefore be handled using air-free techniques.

References

  1. "New Environment Inc. - NFPA Chemicals".
  2. E. Frankland (1850). "On the isolation of the organic radicals". Quarterly Journal of the Chemical Society. 2 (3): 263–296. doi:10.1039/QJ8500200263.
  3. Dietmar Seyferth (2001). "Zinc Alkyls, Edward Frankland, and the Beginnings of Main-Group Organometallic Chemistry". Organometallics. 20 (14): 2940–2955. doi:10.1021/om010439f.
  4. E. Frankland, B. F. Duppa (1864). "On a new reaction for the production of the zinc-compounds of the alkyl-radical". Journal of the Chemical Society. 17: 29–36. doi:10.1039/JS8641700029.
  5. C. R. Noller (1943). "Diethyl Zinc". Organic Syntheses; Collected Volumes, vol. 2, p. 184.
  6. John Bacsa; Felix Hanke; Sarah Hindley; Rajesh Odedra; George R. Darling; Anthony C. Jones; Alexander Steiner (2011). "The Solid State Structures of Dimethylzinc and Diethylzinc". Angewandte Chemie International Edition. 50 (49): 11685–11687. doi:10.1002/anie.201105099. PMC 3326375. PMID 21919175.
  7. A. Haaland; J. C. Green; G. S. McGrady; A. J. Downs; E. Gullo; M. J. Lyall; J. Timberlake (2003). "The length, strength and polarity of metal–carbon bonds: dialkylzinc compounds studied by density functional theory calculations, gas electron diffraction and photoelectron spectroscopy". Dalton Transactions (22): 4356–4366. doi:10.1039/B306840B.
  8. Masato Kitamura, Hiromasa Oka, Seiji Suga, and Ryōji Noyori (2004). "Catalytic Enantioselective Addition of Dialkylzincs to Aldehydes Using (2S)-(−)-3-exo-(Dimethylamino)isoborneol : (S)-1-Phenyl-1-propanol". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 10, p. 635.
  9. Jean-Nicolas Desrosiers, Alexandre Côté, Alessandro A. Boezio, and André B. Charette (2005). "Preparation of Enantiomerically Enriched (1S)-1-Phenylpropan-1-amine Hydrochloride by a Catalytic Addition of Diorganozinc Reagents to Imines". Organic Syntheses. 83: 5{{cite journal}}: CS1 maint: multiple names: authors list (link).
  10. André B. Charette and Hélène Lebel (2004). "(2S,3S)-(+)-(3-Phenylcyclopropyl)methanol". Organic Syntheses; Collected Volumes, vol. 10, p. 613.
  11. Yoshihiko Ito, Shotaro Fujii, Masashi Nakatuska, Fumio Kawamoto, and Takeo Saegusa (1988). "One-Carbon Ring Expansion of Cycloalkanones to Conjugated Cycloalkenones: 2-Cyclohepten-1-one". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 327.
  12. Dmitri V. Talapin; Ivo Mekis; Stephan Götzinger; Andreas Kornowski; Oliver Benson; Horst Weller† (2004). "CdSe/CdS/ZnS and CdSe/ZnSe/ZnS Core−Shell−Shell Nanocrystals". Journal of Physical Chemistry B. 108 (49): 18826–18831. doi:10.1021/jp046481g.
  13. Mitsuo Sawamoto; Chihiro Okamoto; Toshinobu Higashimura (1987). "Hydrogen iodide/zinc iodide: a new initiating system for living cationic polymerization of vinyl ethers at room temperature". Macromolecules. 20 (11): 2693–2697. Bibcode:1987MaMol..20.2693S. doi:10.1021/ma00177a010.
  14. Clark, John Drury (23 May 2018). Ignition!: An Informal History of Liquid Rocket Propellants. Rutgers University Press. p. 302. ISBN 978-0-8135-9918-2. OCLC 281664.
  15. Sutton, George P.; Biblarz, Oscar (2001). Rocket Propulsion Elements - Seventh Edition (PDF). John Wiley & Sons, Inc. ISBN 0-471-32642-9. Archived (PDF) from the original on 28 February 2022.
  16. Kenneth E. Harris; Chandru J. Shahani (2004), Mass Deacidification: An Initiative To Refine The Diethyl Zinc Process (PDF), Washington, D.C.: Library of Congress, archived from the original (PDF) on 2013-05-14
  17. Shriver, Duward F.; Drezdzon, Mark A. (1986). The Manipulation of Air-Sensitive Compounds. John Wiley & Sons. p. 57. ISBN 0-471-86773-X.

External links

Zinc compounds
Zinc(I)
Organozinc(I) compounds
Zinc(II)
Organozinc(II) compounds
  • Zn(CH3)2
  • Zn(C2H5)2
  • Zn(CH3COO)2
  • Zn(CH(CH3)2)2
  • Zn(C(CH3)3)2
  • Zn(C6H5)2
  • Zn(C3H5O3)2
  • ZnICH2I
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