三氯三(四氫呋喃)合鈦(III)

三氯三(四氫呋喃)合鈦(III)
英文名	Trichlorotris(tetrahydrofuran)titanium
識別
CAS號	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
性質
化學式	C12H24Cl3O3Ti
摩爾質量	370.54 g·mol−1
外觀	天藍色固體
密度	1.45 g·cm−3
熔點	分解
溶解性（水）	水解
結構
晶體結構	P21/c
危險性
	GHS危險性符號;
GHS提示詞	危險
H-術語	H228, H314
P-術語	P210, P240, P241, P260, P264, P280, P301+330+331, P303+361+353, P304+340, P305+351+338, P310, P321, P363, P370+378
相關物質
其他陰離子	三溴三(四氫呋喃)合鈦(III)
其他陽離子	三氯三(四氫呋喃)合釩(III)
相關化學品	三氯化鈦
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

三氯三(四氫呋喃)合鈦(III)是一種配位化合物，化學式為C₁₂H₂₄Cl₃O₃Ti，可簡寫為TiCl₃(THF)₃，其中THF為四氫呋喃。它對空氣和水十分敏感。^[3]

製備

三氯三(四氫呋喃)合鈦(III)可由三氯化鈦和過量的四氫呋喃反應得到；^[4]或由3TiCl₃·AlCl₃和四氫呋喃反應製得。^[5]另一種常用的方法是由鋁在THF中還原TiCl₄(THF)₂：^[3]

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

性質

三氯三(四氫呋喃)合鈦(III)在100 °C分解為綠色的TiCl₃(THF)₂，繼續加熱得到灰色的TiCl₃(THF)^[4]，150~200 °C發生歧化反應，生成TiCl₂並升華得到亮黃色的TiCl₄(THF)₂。^[1]

它在四氫呋喃中氬氣氣氛下可以被鎂還原為Ti(MgCl)₂·TiCl₂，它和氮氣反應生成Ti(MgCl)₂(N₂)·TiCl₂，^[6]也有文獻報道這一反應直接在氮氣中進行，得到含Ti–N鍵的另一化合物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體系可以和一氧化碳反應，生成TiC₂並放出甲烷，碳化物水解生成乙炔和甲烷。^[8]

由於三氯三(四氫呋喃)合鈦(III)不穩定，它可以很容易地發生配體取代反應，如它和環辛四烯二鉀在THF中回流反應，部分氯和THF配體被取代，可以結晶出綠色的[C₈H₈TiCl(THF)]₂，它的THF分子可以繼續脫去，得到灰綠色的[C₈H₈TiCl]₄。^[9]三氯三(四氫呋喃)合鈦(III)在室溫下可以和乙酰丙酮反應，生成紅褐色的Ti(acac)Cl₂(THF)₂。^[10]它在乙醚中和五氯苯基鋰反應，可以得到黃色的[Li(THF)₄][Ti(C₆Cl₅)₄]，它在二氯甲烷-乙醚混合溶劑中重結晶，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]⁻

它可以和四氯化鈦、氯化鋅等反應，生成[TiCl₂(THF)₄][SnCl₅(THF)]、[TiCl₂(THF)₄][ZnCl₃(THF)]等。^[12]類似地，它和[NⁿBu₄]₂[MgCl₄]（ⁿBu=正丁基）反應，可以得到藍色的[NⁿBu₄][TiCl₄(THF)₂]·THF。^[13]

用途

三氯三(四氫呋喃)合鈦(III)可用作Ti^III源參與反應，如可以和金屬有機框架材料 MOF-5進行離子交換，得到部分Zn²⁺被Ti³⁺取代的化合物。^[14]

參考文獻

^ ^1.0 ^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. （原始內容存檔於2018-06-13）（英語）.
^ 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 （英語）.
^ ^3.0 ^3.1 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 （英語）.
^ ^4.0 ^4.1 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. （原始內容存檔於2021-08-10）（英語）.
^ 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. （原始內容存檔於2021-07-11）（英語）.
^ 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. （原始內容存檔於2021-08-10）（法語）.
^ 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 （英語）.
^ 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 （英語）.
^ 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 （英語）.
^ 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 （英語）.
^ 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 （英語）.
^ ^12.0 ^12.1 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 （英語）.
^ 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 （英語）.
^ 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 （英語）.

[Kern-1] 1.0 ^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. （原始內容存檔於2018-06-13）（英語）.

[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 （英語）.

[Piotr-3] 3.0 ^3.1 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 （英語）.

[Zikmund-4] 4.0 ^4.1 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. （原始內容存檔於2021-08-10）（英語）.

[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. （原始內容存檔於2021-07-11）（英語）.

[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. （原始內容存檔於2021-08-10）（法語）.

[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 （英語）.

[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 （英語）.

[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 （英語）.

[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 （英語）.

[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 （英語）.

[Zofia-12] 12.0 ^12.1 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 （英語）.

[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 （英語）.

[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 （英語）.

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