四氯二(四氢呋喃)合钛(IV)

四氯二(四氢呋喃)合钛(IV)是一种配位化合物，化学式为C8H16Cl4O2Ti，可简写为TiCl4(THF)2，其中THF为四氢呋喃。它是一种强路易斯酸。 四氯二(四氢呋喃)合钛(IV)可由四氯化钛和四氢呋喃在正己烷（或二氯甲烷）中反应得到。 TiCl4 + 2 THF → TiCl4(THF)2 由于该反应是剧烈放热的，一般不在无溶剂条件下反应。 四氯二(四氢呋喃)合钛(IV)和镁在四氢呋喃中于氩气保护下反应，可以得到[Ti(MgCl)2(THF)]2： 2 TiCl4(THF)2 + 6 Mg + 2 THF → [Ti(MgCl)2(THF)]2 + 2 MgCl2(THF)2 生成的低价钛化合物可以吸收二氧化碳，生成[Ti(OOCH)2MgCl1.5(THF)]，它可以进一步和酸反应，生成甲酸，或和碘乙烷反应，生成甲酸乙酯。 它和镁直接在氮气环境中反应，可以得到TiN(MgCl)2(THF)，它可以再和碘反应，经ITiN(MgCl)2中间体，生成Ti=N(MgCl)。氯化亚锡也能将其还原，生成TiCl3(THF)3和绿色的[TiCl2(THF)4][SnCl5(THF)]： 2 TiCl4(THF)2 + SnCl2 → [trans-TiCl2(THF)4][SnCl5(THF)] + TiCl3(THF)3 四氯二(四氢呋喃)合钛(IV)可以和MgCl2(THF)2（1：2）在THF中反应，析出黄色的[(THF)3Mg(μ-Cl)3Mg(THF)3][TiCl5(THF)]晶体；等摩尔比反应时，生成[(THF)4Mg(μ-Cl)2TiCl4]。 四氯二(四氢呋喃)合钛(IV)可以用作TiIV源合成有机钛化合物，如它和1,4-二(三甲基硅基)环辛四烯二锂反应，可以制得夹心化合物Ti{C8H6[Si(CH3)3]2}2；它在THF中被萘钾还原，形成萘基钛阴离子中间体，加入白磷后发生配体取代反应，以制得含五磷唑的钛阴离子[Ti(P5)2]2−。它也可用作金属有机框架材料的后处理（如金属交换）试剂。 Kern, R.J. Tetrahydrofuran complexes of transition metal chlorides. Journal of Inorganic and Nuclear Chemistry. 1962, 24 (9): 1105–1109. ISSN 0022-1902. doi:10.1016/0022-1902(62)80255-3 （英语）.  Sobota, Piotr; Janas, Zofia. Formation of a nitrogen—carbon bond from N2 and CO. Influence of MgCl2 on the N2 reduction process in the system TiCl4/Mg. Journal of Organometallic Chemistry. 1984, 276 (2): 171–176. ISSN 0022-328X. doi:10.1016/0022-328X(84)80628-2 （英语）.  Manxzer, L. E.; Deaton, Joe; Sharp, Paul; Schrock, R. R. 31. Tetragtdrfuran Complexes of Selected Early Transition Metals.: 135–140. 2007. ISSN 1934-4716. doi:10.1002/9780470132524.ch31 （英语）.  Yoshino, Norio; Yoshino, Takeshi. Syntheses and Reactions of Metal Organics. VII. Reactions ofn-Butoxytitanium Chlorides with Saturated Cyclic Ethers. Bulletin of the Chemical Society of Japan. 1972, 45 (10): 3172–3174. ISSN 0009-2673. doi:10.1246/bcsj.45.3172 （英语）.  Jeżowska-Trzebiatowska, B.; Sobota, P. Fixation of molecular carbon dioxide in the system TiCl4-Mg in tetrahydrofuran under mild conditions. Journal of Organometallic Chemistry. 1974, 76 (1): 43–47. ISSN 0022-328X. doi:10.1016/S0022-328X(00)90313-9 （英语）.  Janas, Zofia; Sobota, Piotr; Lis, Tadeusz. Interaction of titanium and tin chlorides in tetrahydrofuran. The X-ray crystal structure of [trans-TiCl2(THF)4]+[SnCl5(THF)]−. Polyhedron. 1988, 7 (24): 2655–2658. ISSN 0277-5387. doi:10.1016/S0277-5387(00)83888-7 （英语）.  Sobota, Piotr; Utko, Jozef; Lis, Tadeusz. Preparation and crystal structure of tri-p-chloro-hexakis(tetrahydro-furan)dimagnesium(II) pentachloro(tetrahydrofuran)titanate(iv). Journal of the Chemical Society, Dalton Transactions. 1984, (9): 2077. ISSN 0300-9246. doi:10.1039/dt9840002077 （英语）.  Cloke, F. Geoffrey N.; Green, Jennifer C.; Hitchcock, Peter B.; Joseph, Stephen C. P.; Mountford, Philip; Kaltsoyannis, Nikolas; McCamley, Andrew. Molecular and electronic structures of bis[1,4-bis(trimethylsilyl)cyclooctatetraene] sandwich complexes of titanium and zirconium. Journal of the Chemical Society, Dalton Transactions. 1994, (19): 2867. ISSN 0300-9246. doi:10.1039/dt9940002867 （英语）.  Urnėžius, E. A Carbon-Free Sandwich Complex [(P5)2Ti]2-. Science. 2002, 295 (5556): 832–834. ISSN 0036-8075. doi:10.1126/science.1067325 （英语）.  Smith, Stefan J. D.; Konstas, Kristina; Lau, Cher Hon; Gozukara, Yesim M.; Easton, Christopher D.; Mulder, Roger J.; Ladewig, Bradley P.; Hill, Matthew R. Post-Synthetic Annealing: Linker Self-Exchange in UiO-66 and Its Effect on Polymer–Metal Organic Framework Interaction. Crystal Growth & Design. 2017, 17 (8): 4384–4392. ISSN 1528-7483. doi:10.1021/acs.cgd.7b00685 （英语）.  Santaclara, Jara G.; Olivos-Suarez, Alma I.; Gonzalez-Nelson, Adrian; Osadchii, Dmitrii; Nasalevich, Maxim A.; van der Veen, Monique A.; Kapteijn, Freek; Sheveleva, Alena M.; Veber, Sergey L.; Fedin, Matvey V.; Murray, Alexander T.; Hendon, Christopher H.; Walsh, Aron; Gascon, Jorge. Revisiting the Incorporation of Ti(IV) in UiO-type Metal–Organic Frameworks: Metal Exchange versus Grafting and Their Implications on Photocatalysis. Chemistry of Materials. 2017, 29 (21): 8963–8967. ISSN 0897-4756. doi:10.1021/acs.chemmater.7b03320 （英语）.