RT info:eu-repo/semantics/article
T1 Lewis Base Behavior of Bridging Nitrido Ligands of Titanium Polynuclear Complexes
A1 Carbó, Jorge J.
A1 Martínez Espada, Noelia
A1 Mena Montoro, Miguel
A1 González Mosquera, Marta Elena
A1 Poblet Rius, Josep María
A1 Yélamos Sánchez, Carlos
K1 cage compounds
K1 cubanes
K1 density functional calculations
K1 nitrides
K1 titanium
K1 Química
K1 Chemistry
AB The Lewis base behavior of mu(3)-nitrido ligands of the polynuclear titanium complexes [{Ti(eta(5)-C(5)Me(5))(mu-NH)}(3)(mu(3)-N)] (1) and [{Ti(eta(5)-C(5)Me(5))}(4)-(mu(3)-N)(4)] (2) to MX Lewis acids has been observed for the first time. Complex 1 entraps one equivalent of copper(I) halide or copper(I) trifluorornethanesulfonate through the basal NH imido groups to give cube-type adducts [XCu{(mu(3)-NH)(3)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(3)-N)}] (X=Cl (3), Br (4), I (5), OSO(2)CF(3) (6)). However, the treatment of 1 with an excess (>= 2 equiv) of copper reagents afforded complexes [XCu{(mu(3)-NH)(3)Ti(3)(eta(5)-C(5)Me(5))(3)(mu(4)-N)(CuX)}] (X=Cl (7), Br (8), I (9) OSO(2)CF(3) (10)) by incorporation of an additional CuX fragment Lit the mu(3)-N nitrido apical group. Similarly, the tetranuclear cube-type nitrido derivative 2 is capable of incorporating one, two, or up to three CuX units at the mu(3)-N ligands to give complexes [{Ti(eta(5)-C(5)Me(5))}(4)(mu(3)-N)(4-n)-{(mu(4)-N)CuX}(n)] (X=Br (11), n=1; X=Cl (12) n=2; X=OSO(2)CF(3) (13), n=3). Compound 2 also reacts with silver(I) trifluoromethanesulfortate (>= 1 equiv) to give the adduct [{Ti(eta(5)-C(5)Me(5))}(4)(mu(3)-N)(3){(mu(4)-N)AgOSO(2)CF(3)}] (14). X-ray crystal structure determinations have been performed for complexes 8-13. Density functional theory calculations have been carried out to understand the nature and strength of the interactions of [{Ti(eta(5)-C(5)H(5))(mu-NH)}(3)(mu(3)-N)] (1') and [{Ti(eta(5)-C(5)H(5))}(4)-(mu(3)-N)(4)] (2') model complexes with copper and silver MX fragments. Although coordination through the three basal NH imido groups is thermodynamically preferred in the case of V, in both complexes the mu(3)-nitrido groups act as two-electron donor Lewis bases to the appropriate Lewis acids.
SN 0947-6539
YR 2009
FD 2009-11-02
LK http://hdl.handle.net/10017/39008
UL http://hdl.handle.net/10017/39008
LA eng
NO MINISTERIO DE EDUCACIÓN Y CIENCIA, COMUNIDAD DE MADRID, UNIVERSIDAD DE ALCALÁ, GENERALITAT DE CATALUNYA
DS MINDS@UW
RD 25-abr-2024