二茂钛

二茂钛
英文名	titanocene
别名	二(η5-环戊二烯基)钛; 二(π-环戊二烯基)钛
识别
CAS号	1271-29-0
PubChem	92881
SMILES	[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Ti+2];
性质
化学式	C10H10Ti
摩尔质量	178.05 g·mol−1
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

二茂钛是一种有机钛化合物（英语：Organotitanium compound），但未能分离。其化学式为Ti(C₅H₅)₂，可简写为TiCp₂，其中Cp表示环戊二烯阴离子。文献中报道的“二茂钛”为其等效物，即在反应中很可能原位生成活泼的中间体，或这一体系的性质与其相似，这类等效物有“Cp₂TiCl₂+Na或Mg”、“Cp₂TiCl₂+EtMgBr或BuLi”等。^[1]例如，它的等效物“Cp₂TiCl₂+Mg”和一种双环硅基锡烯反应，可以得到[Sn]₂TiCp₂（[Sn]为Si₄Sn环）。^[2]它在有机合成中用作还原剂。^[1]

理论研究表明，它可将小分子醇类或氨基化合物脱氢。^[3]

二茂钛二聚体

二茂钛二聚体的结构

二茂钛二聚体（Ti₂C₂₀H₂₀，CAS号：52676-23-0）可由二甲基二茂钛和氢气反应，或由二氯二茂钛和萘钠或钠沙反应得到。其结构含3c2e的氢桥键，以及两个茂环和一个二聚茂环（富瓦烯环）。^[4]它和氯化氢在醚溶液中反应，桥联氢被氯取代，生成紫色的(C₅H₈)(TiCl(C₅H₄)₂。^[4]它和甲酸或苯甲酸反应，得到[(C₅H₅)Ti(OCOR)₂]₂（R=H, C₆H₅）。^[5]它和二氧化碳反应，根据反应条件，生成甲酸盐(C₅H₈)(Ti(C₅H₄)₂(OCOH)₂，或甲醇盐，仅桥联氢配体被取代。^[6]

参考文献

^ ^1.0 ^1.1 Hirokazu Urabe, Fumie Sato. John Wiley & Sons, Ltd , 编. Titanocene (Cp 2 Ti(II)). Chichester, UK: John Wiley & Sons, Ltd. 2003-04-15 [2022-10-18]. ISBN 9780471936237. doi:10.1002/047084289x.rn00195. （原始内容存档于2022-10-21）（英语）.
^ Henning Arp, Judith Baumgartner, Christoph Marschner, Patrick Zark, Thomas Müller. Coordination Chemistry of Cyclic Disilylated Stannylenes and Plumbylenes to Group 4 Metallocenes. Journal of the American Chemical Society. 2012-07-04, 134 (26): 10864–10875 [2022-10-18]. ISSN 0002-7863. PMC 3396127  . PMID 22716501. doi:10.1021/ja301547x. （原始内容存档于2022-10-21）（英语）.
^ Avik Ghosh, Tamalika Ash, Tanay Debnath, Abhijit K. Das. H2-release from alcohols, diols, and compounds with amino functionality promoted by titanium(II) sandwich complex, [Cp2Ti]: a theoretical approach. Structural Chemistry. 2019-06, 30 (3): 681–690 [2022-10-18]. ISSN 1040-0400. doi:10.1007/s11224-018-1207-0 （英语）.
^ ^4.0 ^4.1 Hans Brintzinger, John E. Bercaw. Nature of so-called titanocene, (C10H10Ti)2. Journal of the American Chemical Society. 1970-10, 92 (21): 6182–6185 [2022-10-26]. ISSN 0002-7863. doi:10.1021/ja00724a013. （原始内容存档于2022-10-26）（英语）.
^ Thomas Wöhrle, Ulf Thewalt. Darstellung und Struktur des dimeren η5-Cyclopentadienyl-titan-diformiats. Journal of Organometallic Chemistry. 1994-04, 468 (1-2): C1–C3 [2022-10-26]. doi:10.1016/0022-328X(94)80063-4. （原始内容存档于2018-06-25）（德语）.
^ Jinfeng Ni, Qingxian Zhou, Diana K Canseco, Tammy R Calhoun, Annette R Graham, Kara L Carreras, Carolyn N Schultz. Transformation of carbon dioxide to methoxide by the complex [(C5H5)Ti]2(μ-H)2(μ-C10H8). Inorganica Chimica Acta. 2000-11, 309 (1-2): 23–27 [2022-10-26]. doi:10.1016/S0020-1693(00)00225-5. （原始内容存档于2018-06-29）（英语）.

[Urabe-1] 1.0 ^1.1 Hirokazu Urabe, Fumie Sato. John Wiley & Sons, Ltd , 编. Titanocene (Cp 2 Ti(II)). Chichester, UK: John Wiley & Sons, Ltd. 2003-04-15 [2022-10-18]. ISBN 9780471936237. doi:10.1002/047084289x.rn00195. （原始内容存档于2022-10-21）（英语）.

[2] Henning Arp, Judith Baumgartner, Christoph Marschner, Patrick Zark, Thomas Müller. Coordination Chemistry of Cyclic Disilylated Stannylenes and Plumbylenes to Group 4 Metallocenes. Journal of the American Chemical Society. 2012-07-04, 134 (26): 10864–10875 [2022-10-18]. ISSN 0002-7863. PMC 3396127  . PMID 22716501. doi:10.1021/ja301547x. （原始内容存档于2022-10-21）（英语）.

[3] Avik Ghosh, Tamalika Ash, Tanay Debnath, Abhijit K. Das. H2-release from alcohols, diols, and compounds with amino functionality promoted by titanium(II) sandwich complex, [Cp2Ti]: a theoretical approach. Structural Chemistry. 2019-06, 30 (3): 681–690 [2022-10-18]. ISSN 1040-0400. doi:10.1007/s11224-018-1207-0 （英语）.

[Brintzinger-4] 4.0 ^4.1 Hans Brintzinger, John E. Bercaw. Nature of so-called titanocene, (C10H10Ti)2. Journal of the American Chemical Society. 1970-10, 92 (21): 6182–6185 [2022-10-26]. ISSN 0002-7863. doi:10.1021/ja00724a013. （原始内容存档于2022-10-26）（英语）.

[5] Thomas Wöhrle, Ulf Thewalt. Darstellung und Struktur des dimeren η5-Cyclopentadienyl-titan-diformiats. Journal of Organometallic Chemistry. 1994-04, 468 (1-2): C1–C3 [2022-10-26]. doi:10.1016/0022-328X(94)80063-4. （原始内容存档于2018-06-25）（德语）.

[6] Jinfeng Ni, Qingxian Zhou, Diana K Canseco, Tammy R Calhoun, Annette R Graham, Kara L Carreras, Carolyn N Schultz. Transformation of carbon dioxide to methoxide by the complex [(C5H5)Ti]2(μ-H)2(μ-C10H8). Inorganica Chimica Acta. 2000-11, 309 (1-2): 23–27 [2022-10-26]. doi:10.1016/S0020-1693(00)00225-5. （原始内容存档于2018-06-29）（英语）.

[1]

[2]

[3]

[4]

[5]

[6]