| Autor: |
del Horno, Estefanía, Jover, Jesús, Mena, Miguel, Pérez‐Redondo, Adrián, Yélamos, Carlos |
| Předmět: |
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| Zdroj: |
Chemistry - A European Journal; 1/19/2022, Vol. 28 Issue 4, p1-11, 11p |
| Abstrakt: |
Low‐valent titanium species were prepared by reaction of [TiCp*X3] (Cp*=η5‐C5Me5; X=Cl, Br, Me) with LiEH4 (E=Al, B) or BH3(thf), and their structures elucidated by experimental and theoretical methods. The treatment of trihalides [TiCp*X3] with LiAlH4 in ethereal solvents (L) leads to the hydride‐bridged heterometallic complexes [{TiCp*(μ‐H)}2{(μ‐H)2AlX(L)}2] (L=thf, X=Cl, Br; L=OEt2, X=Cl). Density functional theory (DFT) calculations for those compounds reveal an open‐shell singlet ground state with a Ti−Ti bond and can be described as titanium(II) species. The theoretical analyses also show strong interactions between the Ti−Ti bond and the empty s orbitals of the Al atom of the AlH2XL fragments, which behave as σ‐accepting (Z‐type) ligands. Analogous reactions of [TiCp*X3] with LiBH4 (2 and 3 equiv.) in tetrahydrofuran at room temperature and at 85 °C lead to the titanium(III) compounds [{TiCp*(BH4)(μ‐X)}2] (X=Cl, Br) and [{TiCp*(BH4)(μ‐BH4)}2], respectively. The treatment of [TiCp*Me3] with 4 and 5 equiv. of BH3(thf) produces the diamagnetic [{TiCp*(BH3Me)}2(μ‐B2H6)] and paramagnetic [{TiCp*(μ‐B2H6)}2] complexes, respectively. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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