二茂镁 - 维基百科,自由的百科全书
二茂镁 | |
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IUPAC名 bis(η5-cyclopentadienyl)magnesium | |
识别 | |
CAS号 | 1284-72-6 ![]() |
PubChem | 11984632 |
ChemSpider | 10628001 |
SMILES |
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InChI |
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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。 |
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
[编辑]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]
- Et2O = 乙醚
性质
[编辑]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]
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
[编辑]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D5d。[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 D5h。[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
[编辑]二茂镁可以用来制备其它茂金属:[16]
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]
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
[编辑]- ^ 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的內容。).
- ^ 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.
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