Chemistry:Organosilver chemistry

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Organosilver chemistry in chemistry of compounds containing a carbon to silver chemical bond.[1] The theme is less developed than organocopper chemistry. The first attempts in organosilver were recorded by Buckton in 1859[2] and by J. A. Wanklyn & L. Carius in 1861.[3] The synthesis of methyl silver was described by Semerano and Riccoboni[4] Poor thermal stability is reflected in decomposition temperatures of AgMe (-50 °C) versus CuMe (-15 °C) and PhAg (74 °C) vs PhCu (100 °C).

Alkyl, alkenyl, aryl derivatives

Phenylsilver can be obtained by reaction of silver nitrate with an trialkylphenyllead compound:

AgNO3 + R3PhPb → PhAg

Alternatively, diphenylzinc may be used:[5]

Ph2Zn + AgNO3 → PhAg + PhZnNO3

Silver mesityl is a tetramer. It is produced by reaction of silver chloride and the Grignard reagent:[6]

AgCl + (CH3)3C6H2MgBr → [(CH3)3C6H2Ag]4 + MgClBr

Silver forms stable complexes with ylides such as triphenylphosphonium methylide:

AgCl + Ph3P=CH2 → AgCl(Ph3P=CH2)

Alkenylsilver compounds are also more stable than their alkylsilver counterparts. Vinylsilver can be obtained by reaction of silver nitrate with tetravinyllead:[7]

AgNO3 + (CH2=CH)4Pb → (CH2=CH)Ag + (CH2=CH)3PbNO3

Fluoroalkyl and alkenyl derivatives

The C-Ag bond is stabilized by perfluoroalkyl ligands:[8]

AgF + CF2=CF(CF3) → AgCF(CF3)2

Following established trends, perfluorinated alkyl and alkenyl derivatives of silver exhibit improved thermal stability. The alkenyl derivatives are generated by the addition of silver fluoride to hexafluorobutyne and tetrafluoroallene.[9]

Organosilver compounds usually have the oxidation state +1. A notable exception is Ag(CF3)4−.

Carbene and CO complexes

Silver forms relatively fragile complexes with CO, including [Ag(CO)n]+ (n = 1, 2, 3).[10]

Silver-NHC complexes are numerous. Some are commonly used to prepare other NHC complexes by displacing labile ligands. For example, the reaction of the bis(NHC)silver(I) complex with bis(acetonitrile)palladium dichloride or chlorido(dimethyl sulfide)gold(I):[11]

Silver-NHC as carbene transmetallation agent.png

Alkene complexes

Structure of the complex between silver nitrate and trans-cyclooctene.[12]

Like other heavy d10 metal ions, Ag+ has a pronounced affinity for alkenes. The ability of silver to form alkene complexes has long been exploited in the separation of alkenes by "argentation chromatography", which uses a support containing silver salts.[13] Illustrative is [Ag(C2H4)3]+.[14]

Catalysis

In catalysis silver is active as silver oxide in the Wolff rearrangement. Silver is also present in other carbon-carbon bond skeletal rearrangements such as the quadricyclane to norbornadiene rearrangement, the cubane to cuneane rearrangement and the rearrangement of the cyclobutadiene dimer to cyclooctatetraene.

Further reading

  • W.A. Herrmann, ed (1999). Synthetic Methods of Organometallic and Inorganic Chemistry. 5, Copper, Silver, Gold, Zinc, Cadmium, and Mercury. Stuttgart: Thieme. ISBN 3-13-103061-5. 
  • Christoph Elschenbroich (2006). Organometallics (3 ed.). Weinheim: Wiley-VCH. ISBN 3-527-29390-6. 
  • The Chemistry of Organic Derivatives of Gold and Silver. Edited by Saul Patai and Zvi Rappoport Copyright 1999 John Wiley & Sons, Ltd. ISBN:0-471-98164-8

References

  1. ↑ Pouwer, Rebecca H.; Williams, Craig M. (2010). "Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic Synthesis". Silver in Organic Chemistry. pp. 1–41. doi:10.1002/9780470597521.ch1. ISBN 9780470597521. 
  2. ↑ Buckton, G. B. (1859). "Untersuchungen über organische Metallverbindungen". Annalen der Chemie und Pharmacie 109 (2): 218–227. doi:10.1002/jlac.18591090216. https://zenodo.org/record/1427125. 
  3. ↑ Wanklyn, J. A.; Carius, L. (1861). "10. Ueber eine neue Wasserstoffverbindung des Eisens". Annalen der Chemie und Pharmacie 120 (1): 69. doi:10.1002/jlac.18611200107. https://zenodo.org/record/1427173. 
  4. ↑ Semerano, G.; Riccoboni, L. (1941). "Beitrag zur Kenntnis der metallorganischen Verbindungen, I. Mitteil.: Silbermethyl, Silber-äthyl und Silber-n-propyl". Berichte der Deutschen Chemischen Gesellschaft (A and B Series) 74 (7): 1089. doi:10.1002/cber.19410740703. 
  5. ↑ Boersma, J; Des Tombe, F.J.A.; Weijers, F.; Van Der Kerk, G.J.M. (1977). "A new, easy synthesis of phenylsilver". J. Organomet. Chem. 124 (2): 229. doi:10.1016/S0022-328X(00)90970-7. 
  6. ↑ Meyer, Edouard Marc.; Gambarotta, Sandro.; Floriani, Carlo.; Chiesi-Villa, Angiola.; Guastini, Carlo. (1989). "Polynuclear Aryl Derivatives of Group 11 metals. Synthesis, Solid State-Solution Structural Rrelationship, and Reactivity with Phosphines". Organometallics 8 (4): 1067–1079. doi:10.1021/om00106a031. 
  7. ↑ Holliday, A; Pendlebury, R.E. (1967). "Vinyllead compounds I. Cleavage of vinyl groups from tetravinyllead". J. Organomet. Chem. 7 (2): 281–284. doi:10.1016/S0022-328X(00)91078-7. 
  8. ↑ Miller, W. T.; Burnard, R. J. (1968). "Perfluoroalkylsilver compounds". J. Am. Chem. Soc. 90 (26): 7367–7368. doi:10.1021/ja01028a047. 
  9. ↑ Burton, Donald J.; Yang, Zhen-Yu; Morken, Peter A. (1994). "Fluorinated organometallics: Vinyl, Alkynyl, Allyl, Benzyl, Propargyl and Aryl". Tetrahedron 50 (10): 2993–3063. doi:10.1016/S0040-4020(01)81105-4. 
  10. ↑ Strauss, Steven H. (2000). "Copper(I) and silver(I) carbonyls. To be or not to be nonclassical". Journal of the Chemical Society, Dalton Transactions: 1–6. doi:10.1039/A908459B. 
  11. ↑ Wang, Harrison M. J.; Lin, Ivan J. B. (1998). "Facile Synthesis of Silver(I)−Carbene Complexes. Useful Carbene Transfer Agents". Organometallics 17 (5): 972. doi:10.1021/om9709704. 
  12. ↑ Rencken, Ilmarie; Boeyens, Jan C. A.; Orchard, S. Walter (1988). "Crystal Structures of the trans-Cyclooctene Complexes of Copper(I) Chloride and Silver Nitrate". Journal of Crystallographic and Spectroscopic Research 18 (3): 293–306. doi:10.1007/BF01194320. 
  13. ↑ Boryana Nikolova-Damyanova. "Principles of Silver Ion Complexation with Double Bonds". https://lipidlibrary.aocs.org/lipid-analysis/silver-ion-chromatography-of-lipids. 
  14. ↑ Fianchini, Mauro; Campana, Charles F.; Chilukuri, Bhaskar; Cundari, Thomas R.; Petricek, Vaclav; Dias, H. V. Rasika (2013). "Use of [SbF6]− to Isolate Cationic Copper and Silver Adducts with More than One Ethylene on the Metal Center". Organometallics 32 (10): 3034–3041. doi:10.1021/om4002439. 




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