二茂镁

二茂镁
	IUPAC名; bis(η5-cyclopentadienyl)magnesium
识别
CAS号	1284-72-6
PubChem	11984632
ChemSpider	10628001
SMILES	[cH-]1cccc1.[cH-]1cccc1.[Mg+2];
InChI	1S/2C5H5.Mg/c21-2-4-5-3-1;/h21-5H;/q2*-1;+2;
EINECS	603-275-0
性质
化学式	C10H10Mg
摩尔质量	154.49 g·mol−1
外观	无色晶体
熔点	176 °C（449 K）（）
沸点	290 °C（563 K）（）
溶解性	与水激烈反应，可溶于极性和非极性溶剂。
危险性
	GHS危险性符号;
GHS提示词	Danger
H-术语	H228, H250, H261, H314
P-术语	P210, P231+232, P280, P303+361+353, P304+340+310, P305+351+338+310, P335+334, P422
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

二茂镁，有时简称 MgCp₂，是一种有机镁化合物，化学式 Mg(η⁵-C₅H₅)₂。它是一种主族夹心配合物，结构类似过渡金属的茂金属，由中心镁原子和两个环戊二烯配体组成。

制备

二茂镁是在1954年由恩斯特·奥托·菲舍尔和杰弗里·威尔金森独立发现的。^[4]^[5]它可以由CpMgBr歧化或是金属镁和环戊二烯在500 °C 下反应而成。对于前者，茂基溴化镁可以由乙基溴化镁和环戊二烯反应而成，然后在220 °C 和10⁻⁴ mbar下分解成MgCp₂ 和MgBr₂：^[6]

\mathrm {Mg(C_{2}H_{5})Br\ {\xrightarrow[{-C_{2}H_{6))]{+C_{5}H_{6},\ Et_{2}O))\ Mg(C_{5}H_{5})Br{\xrightarrow[{-MgBr_{2))]{x2,\ 220^{\circ }C,\ 10^{-4}mbar))\ Mg(C_{5}H_{5})_{2))

Et₂O = 乙醚

\mathrm {Mg\ +\ 2\ C_{5}H_{6}\ {\xrightarrow[{-H_{2))]{500^{\circ }C))\ Mg(C_{5}H_{5})_{2}\ }

在实验室里，可以由二烷基镁和环戊二烯反应得到二茂镁：^[1]

\mathrm {Mg(C_{4}H_{9})_{2}\ +\ 2\ C_{5}H_{6}\ \rightarrow \ Mg(C_{5}H_{5})_{2}\ +\ 2\ C_{4}H_{10}\uparrow \ }

性质

室温下，二茂镁是一种白色固体。^[7]它的熔点为 176 °C，尽管在常压下会在100 °C时升华。^[7]不像二茂铁，二茂镁会在极性、给电子溶剂中（例如醚和THF）会自耦电离：^[8]

{\ce {MgCp2 <=> MgCp+ + Cp-))

{\ce {MgCp2 + MgCp+ <=> Mg2Cp3+))

{\ce {MgCp2 + Cp- <=> MgCp3-))

二茂铁在标准情况下稳定，但二茂镁在氧气或湿气中迅速分解，所以在惰性气氛下制备和储存。^[9]

结构和成键

通过X射线晶体学，固体二茂镁的平均 Mg-C 和C-C键长分别为2.30 Å 和1.39 Å，两个茂环是错位的，点群D_5d。^[10]气相电子衍射显示出相似的键长，不过两个茂环是重叠的，点群 D_5h。^[11]^[12]

关于Mg-Cp 的相互作用主要是离子键^[13]^[14]还是共价键^[11]^[12]^[15]一直存在激烈的争论。

反应性和潜在用处

二茂镁可以用来制备其它茂金属：^[16]

{\ce {MgCp2 + MCl2 -> MCp2 + MgCl2))

在四氢呋喃里，二茂镁会和 MgX₂（X = 卤素）交换配体，形成半夹心化合物CpMgX ：^[17]

{\ce {MgCp2 + MgX2 <=> 2 CpMgX))

反应产生的半夹心化合物可作为从有机卤化物合成取代茂基的原料。^[18]

由于其高反应性，二茂镁是半导体研究中的一个有吸引力的目标，可作为化学气相沉积和掺杂应用的起始材料。^[19]^[20]

二茂镁在下一代的镁离子电池中，有作为电解质的潜在用途。^[8]

参考资料

^ ^1.0 ^1.1 ^1.2 Anja Jaenschke: Basenaddukte des Magnesocens: Darstellung und Strukturuntersuchung von Cyclopentadienyl-, Pentamethylcyclopentadienyl- und Indenyl-Metallocenen des Magnesiums. Dissertation, Uni Hamburg, 2006 Template:URN.
^ W. A. Barber. Eugene G. Rochow , 编. Magnesium cyclopentadienide. McGraw-Hill Book Company, Inc. 1960: 11–15 （英语）.
^ (({2))}. www.chemicalbook.com.
^ E. O. Fischer, W. Hafner: Cyclopentadienyl-vanadin-tetracarbonyl. In: Zeitschrift für Naturforschung B. 9, 1954, S. 503–504 (online).
^ G. Wilkenson, F.A. Cotton, Chem. Ind.(London) 1954, 307–308
^ Christoph Elschenbroich: Organometallchemie. 6. Auflage, Teubner Wiesbaden, 2008, ISBN 978-3-8351-0167-8, S. 65 (《二茂镁》在Google Books的内容。).
^ ^7.0 ^7.1 Barber, W. A.; Jolly, William L., Magnesium Cyclopentadienide, Inorganic Syntheses (John Wiley & Sons, Ltd), 1960: 11–15, ISBN 9780470132371, doi:10.1002/9780470132371.ch5
^ ^8.0 ^8.1 Schwarz, Rainer; Pejic, Marijana; Fischer, Philipp; Marinaro, Mario; Jörissen, Ludwig; Wachtler, Mario. Magnesocene-Based Electrolytes: A New Class of Electrolytes for Magnesium Batteries. Angewandte Chemie International Edition. 2016-11-21, 55 (48): 14958–14962. ISSN 1521-3773. PMID 27791301. doi:10.1002/anie.201606448.
^ Barber, W. A. A new preparation of magnesium cyclopentadienide. Journal of Inorganic and Nuclear Chemistry. 1957-01-01, 4 (5–6): 373–374. ISSN 0022-1902. doi:10.1016/0022-1902(57)80026-8.
^ Bünder, W.; Weiss, E. Verfeinerung der kristallstruktur von dicyclopentadienylmagnesium, (η-C5H5)2Mg [Refinement of the crystal structure of dicyclopentadienylmagnesium, (η5-C5H5)2Mg]. Journal of Organometallic Chemistry. 1975-06-10, 92 (1): 1–6. ISSN 0022-328X. doi:10.1016/S0022-328X(00)91094-5.
^ ^11.0 ^11.1 Starowieyski, Kazimir B.; Brunvoll, Jon; Novak, David P.; Lusztyk, Janusz; Haaland, Arne. Molecular structures of dicyclopentadienylmagnesium and dicyclopentadienylchromium by gas-phase electron diffraction. Journal of the Chemical Society, Chemical Communications. 1974-01-01, (2): 54–55. ISSN 0022-4936. doi:10.1039/C39740000054.
^ ^12.0 ^12.1 Haaland, A.; Lusztyk, J.; Brunvoll, J.; Starowieyski, K. B. On the molecular structure of dicyclopentadienylmagnesium. Journal of Organometallic Chemistry. 1975-02-11, 85 (3): 279–285. ISSN 0022-328X. doi:10.1016/S0022-328X(00)80301-0.
^ Cotton, F. A.; Reynolds, L. T. The Structure and Bonding of Cyclopentadienylthallium and Bis-cyclopentadienylmagnesium. Journal of the American Chemical Society. January 1958, 80 (2): 269–273. ISSN 0002-7863. doi:10.1021/ja01535a004.
^ Aleksanyan, V. T.; Garbuzova, I. A.; Gavrilenko, V. V.; Zakharkin, L. I. Vibrational spectra and structure of bis(cyclopentadienyl)magnesium. Journal of Organometallic Chemistry. 1977-04-12, 129 (2): 139–143. ISSN 0022-328X. doi:10.1016/S0022-328X(00)92483-5.
^ Lippincott, Ellis R.; Xavier, J.; Steele, D. The Vibrational Spectra and Structure of Bis-cyclopentadienylmagnesium. Journal of the American Chemical Society. 1961-05-01, 83 (10): 2262–2266. ISSN 0002-7863. doi:10.1021/ja01471a011.
^ Hull, H. S.; Reid, Allen Forrest; Turnbull, Alan G. Heat of formation and bond energy of bis(cyclopentadienyl)magnesium. Inorganic Chemistry. 1967-04-01, 6 (4): 805–807. ISSN 0020-1669. doi:10.1021/ic50050a032.
^ Ford, Warren T.; Grutzner, John B. Proton and carbon-13 nuclear magnetic resonance spectra of cyclopentadienylmagnesium compounds in tetrahydrofuran. The Journal of Organic Chemistry. 1972-08-01, 37 (16): 2561–2564. ISSN 0022-3263. doi:10.1021/jo00981a009.
^ Dzhemilev, U. M.; Ibragimov, A. G.; Tolstikov, G. A. Synthesis and transformations of "non-grignard" organomagnesium reagents obtained from 1,3-dienes. Journal of Organometallic Chemistry. 1991-03-26, 406 (1–2): 1–47. ISSN 0022-328X. doi:10.1016/0022-328X(91)83169-5.
^ Lundberg, Å; Andersson, S. G.; Landgren, G.; Rask, M. Abruptp- type doping transitions using bis-(cyclopentadienyl)-magnesium in metal-organic vapor phase epitaxy of GaAs. Journal of Electronic Materials. 1988-07-01, 17 (4): 311–314. Bibcode:1988JEMat..17..311R. ISSN 1543-186X. S2CID 97230793. doi:10.1007/BF02652111.
^ Kondo, M.; Anayama, C.; Sekiguchi, H.; Tanahashi, T. Mg-doping transients during metalorgic vapor phase epitaxy of GaAs and AlGaInP. Journal of Crystal Growth. 1994-08-01, 141 (1–2): 1–10. Bibcode:1994JCrGr.141....1K. ISSN 0022-0248. doi:10.1016/0022-0248(94)90085-X.

分类

[Jaenschke-1] 1.0 ^1.1 ^1.2 Anja Jaenschke: Basenaddukte des Magnesocens: Darstellung und Strukturuntersuchung von Cyclopentadienyl-, Pentamethylcyclopentadienyl- und Indenyl-Metallocenen des Magnesiums. Dissertation, Uni Hamburg, 2006 Template:URN.

[IS6-2] W. A. Barber. Eugene G. Rochow , 编. Magnesium cyclopentadienide. McGraw-Hill Book Company, Inc. 1960: 11–15 （英语）.

[Chemicalbook-3] (({2))}. www.chemicalbook.com.

[4] E. O. Fischer, W. Hafner: Cyclopentadienyl-vanadin-tetracarbonyl. In: Zeitschrift für Naturforschung B. 9, 1954, S. 503–504 (online).

[5] G. Wilkenson, F.A. Cotton, Chem. Ind.(London) 1954, 307–308

[Elschenbroich_65-6] Christoph Elschenbroich: Organometallchemie. 6. Auflage, Teubner Wiesbaden, 2008, ISBN 978-3-8351-0167-8, S. 65 (《二茂镁》在Google Books的内容。).

[Barber_1960-7] 7.0 ^7.1 Barber, W. A.; Jolly, William L., Magnesium Cyclopentadienide, Inorganic Syntheses (John Wiley & Sons, Ltd), 1960: 11–15, ISBN 9780470132371, doi:10.1002/9780470132371.ch5

[Schwarz_2016-8] 8.0 ^8.1 Schwarz, Rainer; Pejic, Marijana; Fischer, Philipp; Marinaro, Mario; Jörissen, Ludwig; Wachtler, Mario. Magnesocene-Based Electrolytes: A New Class of Electrolytes for Magnesium Batteries. Angewandte Chemie International Edition. 2016-11-21, 55 (48): 14958–14962. ISSN 1521-3773. PMID 27791301. doi:10.1002/anie.201606448.

[9] Barber, W. A. A new preparation of magnesium cyclopentadienide. Journal of Inorganic and Nuclear Chemistry. 1957-01-01, 4 (5–6): 373–374. ISSN 0022-1902. doi:10.1016/0022-1902(57)80026-8.

[10] Bünder, W.; Weiss, E. Verfeinerung der kristallstruktur von dicyclopentadienylmagnesium, (η-C5H5)2Mg [Refinement of the crystal structure of dicyclopentadienylmagnesium, (η5-C5H5)2Mg]. Journal of Organometallic Chemistry. 1975-06-10, 92 (1): 1–6. ISSN 0022-328X. doi:10.1016/S0022-328X(00)91094-5.

[Starowieyski_1974-11] 11.0 ^11.1 Starowieyski, Kazimir B.; Brunvoll, Jon; Novak, David P.; Lusztyk, Janusz; Haaland, Arne. Molecular structures of dicyclopentadienylmagnesium and dicyclopentadienylchromium by gas-phase electron diffraction. Journal of the Chemical Society, Chemical Communications. 1974-01-01, (2): 54–55. ISSN 0022-4936. doi:10.1039/C39740000054.

[Haaland_1975-12] 12.0 ^12.1 Haaland, A.; Lusztyk, J.; Brunvoll, J.; Starowieyski, K. B. On the molecular structure of dicyclopentadienylmagnesium. Journal of Organometallic Chemistry. 1975-02-11, 85 (3): 279–285. ISSN 0022-328X. doi:10.1016/S0022-328X(00)80301-0.

[13] Cotton, F. A.; Reynolds, L. T. The Structure and Bonding of Cyclopentadienylthallium and Bis-cyclopentadienylmagnesium. Journal of the American Chemical Society. January 1958, 80 (2): 269–273. ISSN 0002-7863. doi:10.1021/ja01535a004.

[14] Aleksanyan, V. T.; Garbuzova, I. A.; Gavrilenko, V. V.; Zakharkin, L. I. Vibrational spectra and structure of bis(cyclopentadienyl)magnesium. Journal of Organometallic Chemistry. 1977-04-12, 129 (2): 139–143. ISSN 0022-328X. doi:10.1016/S0022-328X(00)92483-5.

[15] Lippincott, Ellis R.; Xavier, J.; Steele, D. The Vibrational Spectra and Structure of Bis-cyclopentadienylmagnesium. Journal of the American Chemical Society. 1961-05-01, 83 (10): 2262–2266. ISSN 0002-7863. doi:10.1021/ja01471a011.

[16] Hull, H. S.; Reid, Allen Forrest; Turnbull, Alan G. Heat of formation and bond energy of bis(cyclopentadienyl)magnesium. Inorganic Chemistry. 1967-04-01, 6 (4): 805–807. ISSN 0020-1669. doi:10.1021/ic50050a032.

[17] Ford, Warren T.; Grutzner, John B. Proton and carbon-13 nuclear magnetic resonance spectra of cyclopentadienylmagnesium compounds in tetrahydrofuran. The Journal of Organic Chemistry. 1972-08-01, 37 (16): 2561–2564. ISSN 0022-3263. doi:10.1021/jo00981a009.

[Dzhemilev_1991-18] Dzhemilev, U. M.; Ibragimov, A. G.; Tolstikov, G. A. Synthesis and transformations of "non-grignard" organomagnesium reagents obtained from 1,3-dienes. Journal of Organometallic Chemistry. 1991-03-26, 406 (1–2): 1–47. ISSN 0022-328X. doi:10.1016/0022-328X(91)83169-5.

[19] Lundberg, Å; Andersson, S. G.; Landgren, G.; Rask, M. Abruptp- type doping transitions using bis-(cyclopentadienyl)-magnesium in metal-organic vapor phase epitaxy of GaAs. Journal of Electronic Materials. 1988-07-01, 17 (4): 311–314. Bibcode:1988JEMat..17..311R. ISSN 1543-186X. S2CID 97230793. doi:10.1007/BF02652111.

[20] Kondo, M.; Anayama, C.; Sekiguchi, H.; Tanahashi, T. Mg-doping transients during metalorgic vapor phase epitaxy of GaAs and AlGaInP. Journal of Crystal Growth. 1994-08-01, 141 (1–2): 1–10. Bibcode:1994JCrGr.141....1K. ISSN 0022-0248. doi:10.1016/0022-0248(94)90085-X.

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二茂镁

制备

性质

结构和成键

反应性和潜在用处

参考资料

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二茂镁

IUPAC名 bis(η⁵-cyclopentadienyl)magnesium
识别
CAS号	1284-72-6 ^N
PubChem	11984632
ChemSpider	10628001
SMILES	[cH-]1cccc1.[cH-]1cccc1.[Mg+2]
InChI	1S/2C5H5.Mg/c21-2-4-5-3-1;/h21-5H;/q2*-1;+2
EINECS	603-275-0
性质
化学式	C₁₀H₁₀Mg
摩尔质量	154.49 g·mol⁻¹
外观	无色晶体^[1]
熔点	176 °C（449 K）（^[2]）
沸点	290 °C（563 K）（^[3]）
溶解性	与水激烈反应，可溶于极性和非极性溶剂。^[1]
危险性
GHS危险性符号
GHS提示词	Danger
H-术语	H228, H250, H261, H314
P-术语	P210, P231+232, P280, P303+361+353, P304+340+310, P305+351+338+310, P335+334, P422
若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。