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Diethylzinc

August 29, 2023

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.

Diethylzinc
Names
IUPAC name
diethylzinc
Identifiers
  • 557-20-0 Y
3D model (JSmol)
  • Interactive image
ChEBI
  • CHEBI:51496 Y
ChemSpider
  • 10413128 Y
ECHA InfoCard 100.008.330
EC Number
  • 209-161-3
  • 11185
UNII
  • S0W5NQH7C6
UN number 1366
  • DTXSID4052217
  • InChI=1S/2C2H5.Zn/c2*1-2;/h2*1H2,2H3; Y
    Key: HQWPLXHWEZZGKY-UHFFFAOYSA-N Y
  • InChI=1/2C2H5.Zn/c2*1-2;/h2*1H2,2H3;/rC4H10Zn/c1-3-5-4-2/h3-4H2,1-2H3
    Key: HQWPLXHWEZZGKY-GFXTWEBUAS
  • CC[Zn]CC
Properties
(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)
Reacts
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Flammable, pyrophoric in air, corrosive, reacts with water to release ethane
GHS labelling:
Danger
H225, H250, H260, H302+H312+H332, H314, H410
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)
Health 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
3
W
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)

Synthesis Edit

Edward Frankland first reported the compound in 1848 from zinc and ethyl iodide, the first organozinc compound discovered.[2][3] He improved the synthesis by using diethyl mercury as starting material.[4] 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.[5]

Structure Edit

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)°.[6] The structure of the gas-phase shows a very similar Zn-C distance (195.0(2) pm).[7]

Uses Edit

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[8] and imines.[9] Additionally, it is commonly used in combination with diiodomethane as a Simmons-Smith reagent to convert alkenes into cyclopropyl groups.[10][11] 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.[12] 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.[13]

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[14]: 9 [15]: 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 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 explosions from contact between trace amounts of diethylzinc and 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.[16]

In microelectronics, diethylzinc is used as a doping agent.[citation needed]

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.[17]

Safety Edit

Diethylzinc decomposes violently on contact with water and can spontaneously ignite upon contact with air. It should therefore be handled using inert atmosphere techniques.

References Edit

  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.; Collective Volume, 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 [(2S)-DAIB]: (S)-1-Phenyl-1-propanol". Organic Syntheses.{{cite journal}}: CS1 maint: multiple names: authors list (link); Collective Volume, 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.; Collective Volume, 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); Collective Volume, 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 D. (1972). Ignition! An Informal History of Liquid Rocket Propellants (PDF). Rutgers University Press. ISBN 978-0-8135-0725-5. (PDF) from the original on 10 July 2022.
  15. ^ Sutton, George P.; Biblarz, Oscar (2001). Rocket Propulsion Elements - Seventh Edition (PDF). John Wiley & Sons, Inc. ISBN 0-471-32642-9. (PDF) from the original on 28 February 2022.
  16. ^ Kenneth E. Harris; Chandru J. Shahani (2004), (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 Edit

  • Demonstration of the ignition of diethylzinc in air Video - University of Nottingham

August 29, 2023
diethylzinc, c2h5, highly, pyrophoric, reactive, organozinc, compound, consisting, zinc, center, bound, ethyl, groups, this, colourless, liquid, important, reagent, organic, chemistry, available, commercially, solution, hexanes, heptane, toluene, pure, liquid,. 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 Diethylzinc NamesIUPAC name diethylzincIdentifiersCAS Number 557 20 0 Y3D model JSmol Interactive imageChEBI CHEBI 51496 YChemSpider 10413128 YECHA InfoCard 100 008 330EC Number 209 161 3PubChem CID 11185UNII S0W5NQH7C6UN number 1366CompTox Dashboard EPA DTXSID4052217InChI InChI 1S 2C2H5 Zn c2 1 2 h2 1H2 2H3 YKey HQWPLXHWEZZGKY UHFFFAOYSA N YInChI 1 2C2H5 Zn c2 1 2 h2 1H2 2H3 rC4H10Zn c1 3 5 4 2 h3 4H2 1 2H3Key HQWPLXHWEZZGKY GFXTWEBUASSMILES CC Zn CCPropertiesChemical formula C2H5 2ZnMolar mass 123 50 g molDensity 1 205 g mLMelting point 28 C 18 F 245 K Boiling point 117 C 243 F 390 K Solubility in water ReactsHazardsOccupational safety and health OHS OSH Main hazards Flammable pyrophoric in air corrosive reacts with water to release ethaneGHS labelling PictogramsSignal word DangerHazard statements H225 H250 H260 H302 H312 H332 H314 H410Precautionary 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 P501NFPA 704 fire diamond 143WSafety data sheet SDS External MSDSExcept where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Y verify what is Y N Infobox references Contents 1 Synthesis 2 Structure 3 Uses 4 Safety 5 References 6 External linksSynthesis EditEdward Frankland first reported the compound in 1848 from zinc and ethyl iodide the first organozinc compound discovered 2 3 He improved the synthesis by using diethyl mercury as starting material 4 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 5 Structure EditThe 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 6 The structure of the gas phase shows a very similar Zn C distance 195 0 2 pm 7 Uses EditDespite 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 8 and imines 9 Additionally it is commonly used in combination with diiodomethane as a Simmons Smith reagent to convert alkenes into cyclopropyl groups 10 11 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 12 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 13 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 14 9 15 323 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 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 explosions from contact between trace amounts of diethylzinc and 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 16 In microelectronics diethylzinc is used as a doping agent citation needed 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 17 Safety EditDiethylzinc decomposes violently on contact with water and can spontaneously ignite upon contact with air It should therefore be handled using inert atmosphere techniques References Edit New Environment Inc NFPA Chemicals E Frankland 1850 On the isolation of the organic radicals Quarterly Journal of the Chemical Society 2 3 263 296 doi 10 1039 QJ8500200263 Dietmar Seyferth 2001 Zinc Alkyls Edward Frankland and the Beginnings of Main Group Organometallic Chemistry Organometallics 20 14 2940 2955 doi 10 1021 om010439f 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 C R Noller 1943 Diethyl Zinc Organic Syntheses Collective Volume vol 2 p 184 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 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 Masato Kitamura Hiromasa Oka Seiji Suga and Ryōji Noyori 2004 Catalytic Enantioselective Addition of Dialkylzincs to Aldehydes Using 2S 3 exo Dimethylamino isoborneol 2S DAIB S 1 Phenyl 1 propanol Organic Syntheses a href Template Cite journal html title Template Cite journal cite journal a CS1 maint multiple names authors list link Collective Volume vol 10 p 635 Jean Nicolas Desrosiers Alexandre Cote Alessandro A Boezio and Andre 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 a href Template Cite journal html title Template Cite journal cite journal a CS1 maint multiple names authors list link Andre B Charette and Helene Lebel 2004 2S 3S 3 Phenylcyclopropyl methanol Organic Syntheses Collective Volume vol 10 p 613 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 a href Template Cite journal html title Template Cite journal cite journal a CS1 maint multiple names authors list link Collective Volume vol 6 p 327 Dmitri V Talapin Ivo Mekis Stephan Gotzinger 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 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 Clark John D 1972 Ignition An Informal History of Liquid Rocket Propellants PDF Rutgers University Press ISBN 978 0 8135 0725 5 Archived PDF from the original on 10 July 2022 Sutton George P Biblarz Oscar 2001 Rocket Propulsion Elements Seventh Edition PDF John Wiley amp Sons Inc ISBN 0 471 32642 9 Archived PDF from the original on 28 February 2022 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 Shriver Duward F Drezdzon Mark A 1986 The Manipulation of Air Sensitive Compounds John Wiley amp Sons p 57 ISBN 0 471 86773 X External links EditDemonstration of the ignition of diethylzinc in air Video University of Nottingham Retrieved from https en wikipedia org w index php title Diethylzinc amp oldid 1170981255, wikipedia, wiki, book, books, library,

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