有機銀化合物

有機銀化合物是含有碳-銀鍵的化合物，而有機銀化學則是研究此類化合物的有機金屬化學分支。^[1]這個分支沒有有機銅化學那麼發達。

1859年的Buckton^[2]和1861年的J. A. Wanklyn（英語：J. A. Wanklyn）與Georg Ludwig Carius（英語：Georg Ludwig Carius）^[3]記錄了有機銀化合物的首次合成。甲基銀的合成則是由Semerano和Riccoboni描述的。^[4]有機銀化合物的熱穩定性比有機銅化合物差，可以從它們的分解溫度看出：AgMe（-50 °C）和CuMe（-15 °C）以及PhAg（74 °C）和PhCu（100 °C）。

烷基、烯基和芳基衍生物[編輯]

苯基銀可以通過硝酸銀和三烷基苯基鉛化合物反應而成：

AgNO₃ + R₃PhPb → PhAg

它也可以通過二苯基鋅來合成：^[5]

Ph₂Zn + AgNO₃ → PhAg + PhZnNO₃

均三甲苯基銀的結構是四聚體。它可以通過氯化銀和格氏試劑反應而成：^[6]

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

銀可以和如亞甲基三苯基鏻的葉立德形成穩定的配合物：

AgCl + Ph₃P=CH₂ → AgCl(Ph₃P=CH₂)

銀的烯基化合物要比烷基化合物更穩定。乙烯基銀可以通過硝酸銀和四乙烯基鉛反應而成：^[7]

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

氟代烷基和氟代烯基衍生物[編輯]

C-Ag鍵可以被全氟烷基穩定化：^[8]

AgF + CF₂=CF(CF₃) → AgCF(CF₃)₂

按照趨勢，銀的全氟烷基和全氟烯基衍生物的熱穩定性更高。它的全氟烯基衍生物是通過將氟化銀加成到六氟丁炔（英語：Hexafluorobutyne）和四氟丙二烯而成的。^[9]

通常，有機銀化合物中的銀的氧化態為+1，一個值得注意的例外是+3氧化態的Ag(CF₃)₄⁻。

卡賓和CO配合物[編輯]

銀的一氧化碳配合物相對不穩定。它們的通式為 [Ag(CO)_n]⁺，其中n = 1、2、3。^[10]

銀的穩定卡賓配合物很多。它們可以通過置換不穩定的配體來製備其它穩定卡賓配合物。雙(NHC)銀(I)配合物和雙(乙腈)二氯化鈀（英語：bis(acetonitrile)palladium dichloride）或二甲硫醚氯化亞金的反應就是一個例子，見下圖：^[11]

烯烴配合物[編輯]

類似其它重d¹⁰金屬離子，Ag⁺對烯烴有明顯的親和力。銀可以形成烯烴配合物（英語：Alkene complex）的性質使人們一直通過「銀色譜法（英語：Argentation chromatography）」來分離烯烴，該方法使用含有銀鹽的載體。^[13]

擴展閱讀[編輯]

W.A. Herrmann (編). Synthetic Methods of Organometallic and Inorganic Chemistry. 5, Copper, Silver, Gold, Zinc, Cadmium, and Mercury. Stuttgart: Thieme. 1999. ISBN 3-13-103061-5.
Christoph Elschenbroich. Organometallics 3. Weinheim: Wiley-VCH. 2006. 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

參考資料[編輯]

^ Pouwer, Rebecca H.; Williams, Craig M. Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic Synthesis. Silver in Organic Chemistry. 2010: 1–41. ISBN 9780470597521. doi:10.1002/9780470597521.ch1.
^ Buckton, G. B. Untersuchungen über organische Metallverbindungen. Annalen der Chemie und Pharmacie. 1859, 109 (2): 218–227 [2021-12-22]. doi:10.1002/jlac.18591090216. （原始內容存檔於2021-12-22）.
^ Wanklyn, J. A.; Carius, L. 10. Ueber eine neue Wasserstoffverbindung des Eisens. Annalen der Chemie und Pharmacie. 1861, 120 (1): 69 [2021-12-22]. doi:10.1002/jlac.18611200107. （原始內容存檔於2021-12-22）.
^ Semerano, G.; Riccoboni, L. Beitrag zur Kenntnis der metallorganischen Verbindungen, I. Mitteil.: Silbermethyl, Silber-äthyl und Silber-n-propyl. Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 1941, 74 (7): 1089. doi:10.1002/cber.19410740703.
^ Boersma, J; Des Tombe, F.J.A.; Weijers, F.; Van Der Kerk, G.J.M. A new, easy synthesis of phenylsilver. J. Organomet. Chem. 1977, 124 (2): 229. doi:10.1016/S0022-328X(00)90970-7.
^ Meyer, Edouard Marc.; Gambarotta, Sandro.; Floriani, Carlo.; Chiesi-Villa, Angiola.; Guastini, Carlo. Polynuclear Aryl Derivatives of Group 11 metals. Synthesis, Solid State-Solution Structural Rrelationship, and Reactivity with Phosphines. Organometallics. 1989, 8 (4): 1067–1079. doi:10.1021/om00106a031.
^ Holliday, A; Pendlebury, R.E. Vinyllead compounds I. Cleavage of vinyl groups from tetravinyllead. J. Organomet. Chem. 1967, 7 (2): 281–284. doi:10.1016/S0022-328X(00)91078-7.
^ Miller, W. T.; Burnard, R. J. Perfluoroalkylsilver compounds. J. Am. Chem. Soc. 1968, 90 (26): 7367–7368. doi:10.1021/ja01028a047.
^ Burton, Donald J.; Yang, Zhen-Yu; Morken, Peter A. Fluorinated organometallics: Vinyl, Alkynyl, Allyl, Benzyl, Propargyl and Aryl. Tetrahedron. 1994, 50 (10): 2993–3063. doi:10.1016/S0040-4020(01)81105-4.
^ Strauss, Steven H. Copper(I) and silver(I) carbonyls. To be or not to be nonclassical. Journal of the Chemical Society, Dalton Transactions. 2000: 1–6. doi:10.1039/A908459B.
^ Wang, Harrison M. J.; Lin, Ivan J. B. Facile Synthesis of Silver(I)−Carbene Complexes. Useful Carbene Transfer Agents. Organometallics. 1998, 17 (5): 972. doi:10.1021/om9709704.
^ Rencken, Ilmarie; Boeyens, Jan C. A.; Orchard, S. Walter. Crystal Structures of the trans-Cyclooctene Complexes of Copper(I) Chloride and Silver Nitrate. Journal of Crystallographic and Spectroscopic Research. 1988, 18 (3): 293–306. S2CID 94984101. doi:10.1007/BF01194320.
^ Boryana Nikolova-Damyanova. Principles of Silver Ion Complexation with Double Bonds. [2021-12-22]. （原始內容存檔於2021-10-30）.

[1] Pouwer, Rebecca H.; Williams, Craig M. Silver Alkyls, Alkenyls, Aryls, and Alkynyls in Organic Synthesis. Silver in Organic Chemistry. 2010: 1–41. ISBN 9780470597521. doi:10.1002/9780470597521.ch1.

[2] Buckton, G. B. Untersuchungen über organische Metallverbindungen. Annalen der Chemie und Pharmacie. 1859, 109 (2): 218–227 [2021-12-22]. doi:10.1002/jlac.18591090216. （原始內容存檔於2021-12-22）.

[3] Wanklyn, J. A.; Carius, L. 10. Ueber eine neue Wasserstoffverbindung des Eisens. Annalen der Chemie und Pharmacie. 1861, 120 (1): 69 [2021-12-22]. doi:10.1002/jlac.18611200107. （原始內容存檔於2021-12-22）.

[4] Semerano, G.; Riccoboni, L. Beitrag zur Kenntnis der metallorganischen Verbindungen, I. Mitteil.: Silbermethyl, Silber-äthyl und Silber-n-propyl. Berichte der Deutschen Chemischen Gesellschaft (A and B Series). 1941, 74 (7): 1089. doi:10.1002/cber.19410740703.

[5] Boersma, J; Des Tombe, F.J.A.; Weijers, F.; Van Der Kerk, G.J.M. A new, easy synthesis of phenylsilver. J. Organomet. Chem. 1977, 124 (2): 229. doi:10.1016/S0022-328X(00)90970-7.

[6] Meyer, Edouard Marc.; Gambarotta, Sandro.; Floriani, Carlo.; Chiesi-Villa, Angiola.; Guastini, Carlo. Polynuclear Aryl Derivatives of Group 11 metals. Synthesis, Solid State-Solution Structural Rrelationship, and Reactivity with Phosphines. Organometallics. 1989, 8 (4): 1067–1079. doi:10.1021/om00106a031.

[7] Holliday, A; Pendlebury, R.E. Vinyllead compounds I. Cleavage of vinyl groups from tetravinyllead. J. Organomet. Chem. 1967, 7 (2): 281–284. doi:10.1016/S0022-328X(00)91078-7.

[Miller1968-8] Miller, W. T.; Burnard, R. J. Perfluoroalkylsilver compounds. J. Am. Chem. Soc. 1968, 90 (26): 7367–7368. doi:10.1021/ja01028a047.

[9] Burton, Donald J.; Yang, Zhen-Yu; Morken, Peter A. Fluorinated organometallics: Vinyl, Alkynyl, Allyl, Benzyl, Propargyl and Aryl. Tetrahedron. 1994, 50 (10): 2993–3063. doi:10.1016/S0040-4020(01)81105-4.

[10] Strauss, Steven H. Copper(I) and silver(I) carbonyls. To be or not to be nonclassical. Journal of the Chemical Society, Dalton Transactions. 2000: 1–6. doi:10.1039/A908459B.

[11] Wang, Harrison M. J.; Lin, Ivan J. B. Facile Synthesis of Silver(I)−Carbene Complexes. Useful Carbene Transfer Agents. Organometallics. 1998, 17 (5): 972. doi:10.1021/om9709704.

[12] Rencken, Ilmarie; Boeyens, Jan C. A.; Orchard, S. Walter. Crystal Structures of the trans-Cyclooctene Complexes of Copper(I) Chloride and Silver Nitrate. Journal of Crystallographic and Spectroscopic Research. 1988, 18 (3): 293–306. S2CID 94984101. doi:10.1007/BF01194320.

[13] Boryana Nikolova-Damyanova. Principles of Silver Ion Complexation with Double Bonds. [2021-12-22]. （原始內容存檔於2021-10-30）.

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