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urn:hdl:2445/185091 Low-Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments Del Horno, Estefanía Jover Modrego, Jesús Mena, Miguel Pérez-Redondo, Adrián Yélamos, Carlos Teoria del funcional de densitat Bor Titani Density functionals Boron Titanium Low-valent titanium species were prepared by reaction of [TiCp*X3 ] (Cp*=η5 -C5 Me5 ; 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)2 AlX(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 AlH2 XL 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*(BH3 Me)}2 (μ-B2 H6 )] and paramagnetic [{TiCp*(μ-B2 H6 )}2 ] complexes, respectively. 2022-04-22T15:00:18Z 2023-01-19T06:10:25Z 2022-01-19 2022-04-22T15:00:18Z info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Versió postprint del document publicat a: https://doi.org/10.1002/chem.202103085 Chemistry-A European Journal, 2022, vol. 28, num. 4 https://doi.org/10.1002/chem.202103085 (c) Wiley-VCH, 2022 info:eu-repo/semantics/openAccess Wiley-VCH Articles publicats en revistes (Química Inorgànica i Orgànica)