四氯二(四氢呋喃)合钛(IV)

四氯二(四氢呋喃)合钛(IV)
英文名	Tetrachlorobis(tetrahydrofuran)titanium
别名	四氯二(四氢呋喃)合钛
识别
CAS号	31011-57-1
PubChem	10958563
SMILES	C1CCOC1.C1CCOC1.Cl[Ti](Cl)(Cl)Cl;
InChI	1S/2C4H8O.4ClH.Ti/c21-2-4-5-3-1;;;;;/h21-4H2;4*1H;/q;;;;;;+4/p-4;
InChIKey	LXWBMENBONGPSB-UHFFFAOYSA-J
性质
化学式	C8H16Cl4O2Ti
摩尔质量	333.89 g·mol−1
外观	黄色固体
熔点	118 °C（391 K）
溶解性	易溶于四氢呋喃
危险性
	GHS危险性符号;
GHS提示词	危险
H-术语	H228, H314
P-术语	P210, P240, P241, P260, P264, P280, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P363, P370+378
相关物质
其他阴离子	四溴二(四氢呋喃)合钛(IV)
其他阳离子	四氯二(四氢呋喃)合锆(IV); 四氯二(四氢呋喃)合铪(IV)
相关化学品	四氯化钛
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

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。^[2]

制备

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^[3]）中反应得到。^[4]

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。^[3]

性质

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)₂MgCl_1.5(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。^[5]

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)。^[2]氯化亚锡也能将其还原，生成TiCl₃(THF)₃和绿色的[TiCl₂(THF)₄][SnCl₅(THF)]：^[6]

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；^[7]等摩尔比反应时，生成[(THF)₄Mg(μ-Cl)₂TiCl₄]。^[2]

应用

四氯二(四氢呋喃)合钛(IV)可以用作Ti^IV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；^[8]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⁻。^[9]它也可用作金属有机框架材料的后处理（如金属交换）试剂。^[10]^[11]

参考文献

^ ^1.0 ^1.1 ^1.2 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）.
^ ^2.0 ^2.1 ^2.2 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）.
^ ^3.0 ^3.1 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）.

[Kern-1] 1.0 ^1.1 ^1.2 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）.

[Piotr-2] 2.0 ^2.1 ^2.2 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）.

[Manzer-3] 3.0 ^3.1 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）.

[4] 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）.

[5] 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）.

[6] 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）.

[7] 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）.

[8] 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）.

[9] 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）.

[10] 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）.

[11] 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）.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]