三氯三(四氢呋喃)合钛(III)

三氯三(四氢呋喃)合钛(III)
英文名	Trichlorotris(tetrahydrofuran)titanium
识别
CAS号	18039-90-2
PubChem	6097232
SMILES	Cl[Ti](Cl)Cl.C1CCOC1.C2CCOC2.C3CCOC3;
InChI	1S/3C4H8O.3ClH.Ti/c31-2-4-5-3-1;;;;/h31-4H2;3*1H;/q;;;;;;+3/p-3;
InChIKey	MIDYWIPTCYRMQF-UHFFFAOYSA-K
性质
化学式	C12H24Cl3O3Ti
摩尔质量	370.54 g·mol−1
外观	天蓝色固体
密度	1.45 g·cm−3
熔点	分解
溶解性（水）	水解
结构
晶体结构	P21/c
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	三溴三(四氢呋喃)合钛(III)
其他阳离子	三氯三(四氢呋喃)合钒(III)
相关化学品	三氯化钛
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

三氯三(四氢呋喃)合钛(III)是一种配位化合物，化学式为C₁₂H₂₄Cl₃O₃Ti，可简写为TiCl₃(THF)₃，其中THF为四氢呋喃。它对空气和水十分敏感。^[3]

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三氯三(四氢呋喃)合钛(III)可由三氯化钛和过量的四氢呋喃反应得到；^[4]或由3TiCl₃·AlCl₃和四氢呋喃反应制得。^[5]另一种常用的方法是由铝在THF中还原TiCl₄(THF)₂：^[3]

3 TiCl₄(THF)₂ + Al + 5 THF → 3 TiCl₃(THF)₃ + AlCl₃(THF)₂

性质

三氯三(四氢呋喃)合钛(III)在100 °C分解为绿色的TiCl₃(THF)₂，继续加热得到灰色的TiCl₃(THF)^[4]，150~200 °C发生歧化反应，生成TiCl₂并升华得到亮黄色的TiCl₄(THF)₂。^[1]

它在四氢呋喃中氩气气氛下可以被镁还原为Ti(MgCl)₂·TiCl₂，它和氮气反应生成Ti(MgCl)₂(N₂)·TiCl₂，^[6]也有文献报道这一反应直接在氮气中进行，得到含Ti–N键的另一化合物TiN(MgCl)₂·THF：^[7]

2 TiCl₃(THF)₃ + 5 Mg + N₂ → 2 TiN(MgCl)₂·THF + MgCl₂(THF)₂

TiCl₃(THF)₃–Mg–THF体系可以和一氧化碳反应，生成TiC₂并放出甲烷，碳化物水解生成乙炔和甲烷。^[8]

由于三氯三(四氢呋喃)合钛(III)不稳定，它可以很容易地发生配体取代反应，如它和环辛四烯二钾在THF中回流反应，部分氯和THF配体被取代，可以结晶出绿色的[C₈H₈TiCl(THF)]₂，它的THF分子可以继续脱去，得到灰绿色的[C₈H₈TiCl]₄。^[9]三氯三(四氢呋喃)合钛(III)在室温下可以和乙酰丙酮反应，生成红褐色的Ti(acac)Cl₂(THF)₂。^[10]它在乙醚中和五氯苯基锂反应，可以得到黄色的[Li(THF)₄][Ti(C₆Cl₅)₄]，它在二氯甲烷-乙醚混合溶剂中重结晶，部分THF被取代，得到[Li(THF)₂(O(C₂H₅)₂)₂][Ti(C₆Cl₅)₄]·CH₂Cl₂。^[11]

它在THF中存在以下平衡：^[12]

2 TiCl₃(THF)₃ ⇌ [TiCl₂(THF)₄]⁺ + [TiCl₄(THF)₂]⁻

它可以和四氯化钛、氯化锌等反应，生成[TiCl₂(THF)₄][SnCl₅(THF)]、[TiCl₂(THF)₄][ZnCl₃(THF)]等。^[12]类似地，它和[NⁿBu₄]₂[MgCl₄]（ⁿBu=正丁基）反应，可以得到蓝色的[NⁿBu₄][TiCl₄(THF)₂]·THF。^[13]

用途

三氯三(四氢呋喃)合钛(III)可用作Ti^III源参与反应，如可以和金属有机框架材料 MOF-5进行离子交换，得到部分Zn²⁺被Ti³⁺取代的化合物。^[14]

参考文献

[1]
R.J. Kern. Tetrahydrofuran complexes of transition metal chlorides. Journal of Inorganic and Nuclear Chemistry. 1962-12, 24 (9): 1105–1109 [2021-08-03]. doi:10.1016/0022-1902(62)80255-3. （原始内容存档于2018-06-13）（英语）.
[2]
Handlovič, M.; Mikloš, D.; Zikmund, M. The structure of trichlorotris(tetrahydrofuran)titanium(III). Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 1981, 37 (4): 811–814. ISSN 0567-7408. doi:10.1107/S056774088100438X （英语）.
[3]
Sobota, Piotr; Ejfler, Jolanta; Szafert, Sławomir; Szczegot, Krzysztof; Sawka-Dobrowolska, Wanda. New intermediates for the synthesis of olefin polymerization catalysts: the complexes [M2(µ-Cl)2Cl4(thf)4](M = Ti or V, thf = tetrahydrofuran); crystal structures and properties. J. Chem. Soc., Dalton Trans. 1993, (15): 2353–2357. ISSN 0300-9246. doi:10.1039/DT9930002353 （英语）.
[4]
Zikmund, Miroslav; Valent, Aladar; Hrnciarova, Klara; Kohutova, Maria. Synthesis, thermogravimetric, and magnetochemical investigation of chloro (tetrahydrofuran)titanium(III) complexes. Chemicke Zvesti (Chemical Papers). 1969, 23 (11-12): 843–849 [2021-08-10]. ISSN 0366-6352. （原始内容存档于2021-08-10）（英语）.
[5]
Natalie A. Jones, Stephen T. Liddle, Claire Wilson, Polly L. Arnold. Titanium(III) Alkoxy-N-heterocyclic Carbenes and a Safe, Low-Cost Route to TiCl 3 (THF) 3. Organometallics. 2007-01, 26 (3): 755–757 [2021-08-03]. ISSN 0276-7333. doi:10.1021/om060486d. （原始内容存档于2021-07-11）（英语）.
[6]
Tyrlik, Stanislaw; Wolochowicz, Iwona. Investigations on a nitrogen fixing system formed from titanium trichloride.3THF + magnesium in an argon atmosphere. I. Reaction with water and molecular nitrogen. Bulletin de l'Academie Polonaise des Sciences, Serie des Sciences Chimiques. 1976, 24 (5): 341–348 [2021-08-10]. ISSN 0001-4095. （原始内容存档于2021-08-10）（法语）.
[7]
Yamamoto, Akio; Go, Shigeo; Ookawa, Masaharu; Takahashi, Mitsuaki; Ikeda, Sakuji; Keii, Tominaga. Kinetics and Stoichiometry of Nitrogen Fixation with TiCl3-Mg and VCL3-Mg in Tetrahydrofuran. Bulletin of the Chemical Society of Japan. 1972, 45 (10): 3110–3117. ISSN 0009-2673. doi:10.1246/bcsj.45.3110 （英语）.
[8]
Jezowska-Trzebiatowska, B.; Sobota, P. Fixation of the carbon monoxide in the system TiCl₃ · 3THF + Mg + THF. Journal of Organometallic Chemistry. 1973, 61: C43–C44. ISSN 0022-328X. doi:10.1016/S0022-328X(00)86519-5 （英语）.
[9]
van der Wal, H.R.; Overzet, F.; van Oven, H.O.; de Boer, J.L.; de Liefde Meijer, H.J.; Jellinek, F. Cyclooctatetraenetitanium chloride and its adducts with THF and some amines. Journal of Organometallic Chemistry. 1975, 92 (3): 329–340. ISSN 0022-328X. doi:10.1016/S0022-328X(00)85684-3 （英语）.
[10]
Bowden, Frank L.; Ferguson, David. Mixed ligand diketonate complexes of tervalent titanium. Inorganica Chimica Acta. 1978, 26: 251–254. ISSN 0020-1693. doi:10.1016/S0020-1693(00)87223-0 （英语）.
[11]
Alonso, Pablo J.; Forniés, Juan; García-Monforte, M. Angeles; Martín, Antonio; Menjón, Babil. The first structurally characterised homoleptic σ-organotitanium(iii) compound. Chemical Communications. 2002, (7): 728–729. ISSN 1359-7345. doi:10.1039/b111127b （英语）.
[12]
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）.
[13]
Sobota, Piotr; Mustafa, Muhi O.; Lis, Tadeusz. Reaction between the [MgCl4]2− anion and titanium chlorides. The crystal structure of [NBu4][trans-TiCl4(THF)2·THF. Polyhedron. 1989, 8 (16): 2013–2016. ISSN 0277-5387. doi:10.1016/S0277-5387(00)80496-9 （英语）.
[14]
Brozek, Carl K.; Dincă, Mircea. Ti³⁺, V^2+/3+, Cr^2+/3+, Mn²⁺, and Fe²⁺-Substituted MOF-5 and Redox Reactivity in Cr- and Fe-MOF-5. Journal of the American Chemical Society. 2013, 135 (34): 12886–12891. ISSN 0002-7863. doi:10.1021/ja4064475 （英语）.

[Kern-1] [1]
R.J. Kern. Tetrahydrofuran complexes of transition metal chlorides. Journal of Inorganic and Nuclear Chemistry. 1962-12, 24 (9): 1105–1109 [2021-08-03]. doi:10.1016/0022-1902(62)80255-3. （原始内容存档于2018-06-13）（英语）.

[2] [2]
Handlovič, M.; Mikloš, D.; Zikmund, M. The structure of trichlorotris(tetrahydrofuran)titanium(III). Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 1981, 37 (4): 811–814. ISSN 0567-7408. doi:10.1107/S056774088100438X （英语）.

[Piotr-3] [3]
Sobota, Piotr; Ejfler, Jolanta; Szafert, Sławomir; Szczegot, Krzysztof; Sawka-Dobrowolska, Wanda. New intermediates for the synthesis of olefin polymerization catalysts: the complexes [M2(µ-Cl)2Cl4(thf)4](M = Ti or V, thf = tetrahydrofuran); crystal structures and properties. J. Chem. Soc., Dalton Trans. 1993, (15): 2353–2357. ISSN 0300-9246. doi:10.1039/DT9930002353 （英语）.

[Zikmund-4] [4]
Zikmund, Miroslav; Valent, Aladar; Hrnciarova, Klara; Kohutova, Maria. Synthesis, thermogravimetric, and magnetochemical investigation of chloro (tetrahydrofuran)titanium(III) complexes. Chemicke Zvesti (Chemical Papers). 1969, 23 (11-12): 843–849 [2021-08-10]. ISSN 0366-6352. （原始内容存档于2021-08-10）（英语）.

[5] [5]
Natalie A. Jones, Stephen T. Liddle, Claire Wilson, Polly L. Arnold. Titanium(III) Alkoxy-N-heterocyclic Carbenes and a Safe, Low-Cost Route to TiCl 3 (THF) 3. Organometallics. 2007-01, 26 (3): 755–757 [2021-08-03]. ISSN 0276-7333. doi:10.1021/om060486d. （原始内容存档于2021-07-11）（英语）.

[6] [6]
Tyrlik, Stanislaw; Wolochowicz, Iwona. Investigations on a nitrogen fixing system formed from titanium trichloride.3THF + magnesium in an argon atmosphere. I. Reaction with water and molecular nitrogen. Bulletin de l'Academie Polonaise des Sciences, Serie des Sciences Chimiques. 1976, 24 (5): 341–348 [2021-08-10]. ISSN 0001-4095. （原始内容存档于2021-08-10）（法语）.

[7] [7]
Yamamoto, Akio; Go, Shigeo; Ookawa, Masaharu; Takahashi, Mitsuaki; Ikeda, Sakuji; Keii, Tominaga. Kinetics and Stoichiometry of Nitrogen Fixation with TiCl3-Mg and VCL3-Mg in Tetrahydrofuran. Bulletin of the Chemical Society of Japan. 1972, 45 (10): 3110–3117. ISSN 0009-2673. doi:10.1246/bcsj.45.3110 （英语）.

[8] [8]
Jezowska-Trzebiatowska, B.; Sobota, P. Fixation of the carbon monoxide in the system TiCl₃ · 3THF + Mg + THF. Journal of Organometallic Chemistry. 1973, 61: C43–C44. ISSN 0022-328X. doi:10.1016/S0022-328X(00)86519-5 （英语）.

[9] [9]
van der Wal, H.R.; Overzet, F.; van Oven, H.O.; de Boer, J.L.; de Liefde Meijer, H.J.; Jellinek, F. Cyclooctatetraenetitanium chloride and its adducts with THF and some amines. Journal of Organometallic Chemistry. 1975, 92 (3): 329–340. ISSN 0022-328X. doi:10.1016/S0022-328X(00)85684-3 （英语）.

[10] [10]
Bowden, Frank L.; Ferguson, David. Mixed ligand diketonate complexes of tervalent titanium. Inorganica Chimica Acta. 1978, 26: 251–254. ISSN 0020-1693. doi:10.1016/S0020-1693(00)87223-0 （英语）.

[11] [11]
Alonso, Pablo J.; Forniés, Juan; García-Monforte, M. Angeles; Martín, Antonio; Menjón, Babil. The first structurally characterised homoleptic σ-organotitanium(iii) compound. Chemical Communications. 2002, (7): 728–729. ISSN 1359-7345. doi:10.1039/b111127b （英语）.

[Zofia-12] [12]
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）.

[13] [13]
Sobota, Piotr; Mustafa, Muhi O.; Lis, Tadeusz. Reaction between the [MgCl4]2− anion and titanium chlorides. The crystal structure of [NBu4][trans-TiCl4(THF)2·THF. Polyhedron. 1989, 8 (16): 2013–2016. ISSN 0277-5387. doi:10.1016/S0277-5387(00)80496-9 （英语）.

[14] [14]
Brozek, Carl K.; Dincă, Mircea. Ti³⁺, V^2+/3+, Cr^2+/3+, Mn²⁺, and Fe²⁺-Substituted MOF-5 and Redox Reactivity in Cr- and Fe-MOF-5. Journal of the American Chemical Society. 2013, 135 (34): 12886–12891. ISSN 0002-7863. doi:10.1021/ja4064475 （英语）.

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