RT info:eu-repo/semantics/article
T1 Molecular Nitrides with Titanium and Rare-Earth Metals
A1 Caballo González, Jorge
A1 García Castro, María
A1 Martín Alonso, Avelino
A1 Mena Montoro, Miguel
A1 Pérez Redondo, Adrián
A1 Yélamos Sánchez, Carlos
K1 Química
K1 Chemistry
AB A series of titanium-group 3/lanthanide metal complexes have been prepared by reaction of [{Ti(eta(5)-C5Me5)(mu-NH)}(3)(mu(3)-N)] (1) with halide, triflate, or amido derivatives of the rare-earth metals. Treatment of 1 with metal halide complexes [MCl3(thf)(n)] or metal trifluoromethanesulfonate derivatives [M(O3SCF3)(3)] at room temperature affords the cube-type adducts [X3M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (X = Cl, M = Sc (2), Y (3), La (4), Sm (5), Er (6), Lu (7); X = OTf, M = Y (8), Sm (9), Er (10)). Treatment of yttrium (3) and lanthanum (4) halide complexes with 3 equiv of lithium 2,6-dimethylphenoxido [LiOAr] produces the aryloxido complexes [(ArO)(3)M{(mu(3)-NH)(3)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (M = Y (11), La (12)). Complex 1 reacts with 0.5 equiv of rare-earth bis(trimethylsilyl)amido derivatives [M{N(SiMe3)(2)}(3)] in toluene at 85-180 degrees C to afford the corner-shared double-cube nitrido compounds [M(mu(3)-N)(3)(mu(3)-NH)(3){Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}(2)] (M = Sc (13), Y (14), La (15), Sm (16), Eu (17), Er (18), Lu (19)) via NH(SiMe3)(2) elimination. A single-cube intermediate [{(Me3Si)(2)N}Sc{(mu(3)-N)(2)(mu(3)-NH)Ti-3(eta(5)-C5Me5)(3)(mu(3)-N)}] (20) was obtained by the treatment of 1 with 1 equiv of the scandium bis(trimethylsilyl)amido derivative [Sc{N(SiMe3)(2)}(3)]. The X-ray crystal structures of 2, 7, 11, 14, 15, and 19 have been determined. The thermal decomposition in the solid state of double-cube nitrido complexes 14, 15, and 18 has been investigated by thermogravimetric analysis (TGA) and differential thermal analysis (DTA) measurements, as well as by pyrolysis experiments at 1100 degrees C under different atmospheres (Ar, H-2/N-2, NH3) for the yttrium complex 14.
SN 0020-1669
YR 2011
FD 2011-07-18
LK http://hdl.handle.net/10017/38566
UL http://hdl.handle.net/10017/38566
LA eng
NO Ministerio de Educación y Ciencia de España, Comunidad de Madrid, Universidad de Alcalá
DS MINDS@UW
RD 06-dic-2023