RT info:eu-repo/semantics/article T1 Low-Valent Titanium Species Stabilized with Aluminum/Boron Hydride Fragments. A1 Horno Martín, Estefanía del A1 Jover, Jesús A1 Mena Montoro, Miguel A1 Pérez Redondo, Adrián A1 Yélamos Sánchez, Carlos K1 aluminum K1 boron K1 density functional calculations K1 reduction K1 titanium K1 Química K1 Chemistry AB Low-valent titanium species were prepared by reaction of [TiCp*X3] (Cp* = eta5-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*(mu-H)}2{(mu-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 sigma-accepting (Z-type) ligands. Analogous reactions of [TiCp*X3] with LiBH4 (2 and 3 equiv) in tetrahydrofuran at room temperature and at 85 ºC lead to the titanium(III) compounds [{TiCp*(BH4)(mu-X)}2] (X = Cl, Br) and [{TiCp*(BH4)(mu-BH4)}2], respectively. The treatment of [TiCp*Me3] with 4 and 5 equiv of BH3(thf) produces the diamagnetic [{TiCp*(BH3Me)}2(mu-B2H6)] and paramagnetic [{TiCp*(mu-B2H6)}2] complexes, respectively. SN 0947-6539 YR 2022 FD 2022-01-19 LK http://hdl.handle.net/10017/50672 UL http://hdl.handle.net/10017/50672 LA eng NO Ministerio de Ciencia, Innovación y Universidades DS MINDS@UW RD 29-mar-2024