| Autor: |
Caballo, Jorge, Calvo-Molina, Adrián, Claramonte, Sergio, Greño, Maider, Pérez-Redondo, Adrián, Yélamos, Carlos |
| Předmět: |
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| Zdroj: |
Dalton Transactions: An International Journal of Inorganic Chemistry; 3/14/2024, Vol. 53 Issue 10, p4844-4855, 12p |
| Abstrakt: |
The redox chemistry of cube-type titanium(IV) nitrido complexes [{Ti4(η5-C5Me5)3(R)}(μ3-N)4] (R = η5-C5Me5 (1), N(SiMe3)2 (2), η5-C5H4SiMe3 (3), and η5-C5H5 (4)) was investigated by electrochemical methods and chemical reactions. Cyclic voltammetry studies indicate that 1–4 undergo a reversible one-electron reduction at ca. −1.8 V vs. ferrocenium/ferrocene. Thus, complex 1 reacts with sodium sand in tetrahydrofuran to produce the highly reactive ionic compound [Na(thf)6][{Ti(η5-C5Me5)}4(μ3-N)4] (5). The treatment of complexes 1–4 in toluene with one equivalent of [K(C5Me5)] in the presence of macrocycles (L) leads to C10Me10 and the formation of more stable derivatives [K(L)][{Ti4(η5-C5Me5)3(R)}(μ3-N)4] (R = η5-C5Me5, L = 18-crown-6 (6), crypt-222 (7); R = N(SiMe3)2, L = 18-crown-6 (8), crypt-222 (9); R = η5-C5H4SiMe3, L = 18-crown-6 (10), crypt-222 (11); R = η5-C5H5, L = crypt-222 (12)). However, the analogous reaction of 4 with [K(C5Me5)] and 18-crown-6 affords [{(18-crown-6)K}2(μ–η5:η5-C5H5)][{Ti4(η5-C5Me5)3(η5-C5H5)}(μ3-N)4] (13) via abstraction of one cyclopentadienide group from a putative intermediate [(18-crown-6)K(μ–η5:η5-C5H5)Ti4(η5-C5Me5)3(μ3-N)4]. In contrast to the cube-type nitrido systems 1–4, the cyclic voltammogram of the trinuclear imido-nitrido titanium(IV) complex [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] (14) does not reveal any reversible redox event and 14 readily reacts with [K(C5Me5)] to afford C5Me5H and the diamagnetic derivative [{K(μ4-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}2] (15). The treatment of 15 with two equiv. of 18-crown-6 polyethers produces the molecular species [(L)K{(μ3-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}] (L = 18-crown-6 (16), dibenzo-18-crown-6 (17)). Complex 17 further reacts with one equiv. of dibenzo-18-crown-6 to yield the ion-separated compound [K(dibenzo-18-crown-6)2][Ti3(η5-C5Me5)3(μ3-N)(μ-N)(μ-NH)2] (18) similar to the ion pair [K(crypt-222)][Ti3(η5-C5Me5)3(μ3-N)(μ-N)(μ-NH)2] (19) obtained in the treatment of 15 with cryptand-222. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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