Cube-Type Nitrido Complexes Containing Titanium and Zinc/Copper
dataset
posted on 2006-08-21, 00:00 authored by Avelino Martín, Noelia Martínez-Espada, Miguel Mena, Adrián Pérez-Redondo, Carlos YélamosSeveral azaheterometallocubane complexes containing [MTi3N4] cores have been prepared by the reaction of [{Ti(η5-C5Me5)(μ-NH)}3(μ3-N)] (1) with zinc(II) and copper(I) derivatives. The treatment of 1 with zinc dichloride in toluene
at room temperature produces the adduct [Cl2Zn{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}] (2). Attempts to crystallize 2 in
dichloromethane gave yellow crystals of the ammonia adduct [(H3N)Cl2Zn{(μ3-NH)Ti3(η5-C5Me5)3(μ-NH)2(μ3-N)}]
(3). The analogous reaction of 1 with alkyl, (trimethylsilyl)cyclopentadienyl, or amido zinc complexes [ZnR2] leads
to the cube-type derivatives [RZn{(μ3-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}] (R = CH2SiMe3 (5), CH2Ph (6), Me (7),
C5H4SiMe3 (8), N(SiMe3)2 (9)) via RH elimination. The amido complex 9 decomposes in the presence of ambient
light to generate the alkyl derivative [{Me3Si(H)N(Me)2SiCH2}Zn{(μ3-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}] (10). The
chloride complex 2 reacts with lithium cyclopentadienyl or lithium indenyl reagents to give the cyclopentadienyl or
indenyl zinc derivatives [RZn{(μ3-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}] (R = C5H5 (11), C9H7 (12)). Treatment of 1
with copper(I) halides in toluene at room temperature leads to the adducts [XCu{(μ3-NH)3Ti3(η5-C5Me5)3(μ3-N)}]
(X = Cl (13), I (14)). Complex 13 reacts with lithium bis(trimethylsilyl)amido in toluene to give the precipitation of
[{Cu(μ4-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}2] (15). Complex 15 is prepared in a higher yield through the reaction of
1 with [{CuN(SiMe3)2}4] in toluene at 150 °C. The addition of triphenylphosphane to 15 in toluene produces the
single-cube compound [(Ph3P)Cu{(μ3-N)(μ3-NH)2Ti3(η5-C5Me5)3(μ3-N)}] (16). The X-ray crystal structures of 3, 8,
9, and 15 have been determined.
