0000000000194735
AUTHOR
Iván Dorado
Synthesis, Structural Characterisation and Reactivity of New Dinuclear Monocyclopentadienyl Imidoniobium and ‐tantalum Complexes − X‐ray Crystal Structures of [{Nb(η 5 ‐C 5 H 4 SiMe 3 )Cl 2 } 2 (μ‐1,4‐NC 6 H 4 N)], [{Ta(η 5 ‐C 5 Me 5 )Cl 2 } 2 (μ‐1,4‐NC 6 H 4 N)] and [{Ta(η 5 ‐C 5 Me 5 )(CH 2 SiMe 3 ) 2 } 2 (μ‐1,4‐NC 6 H 4 N)]
The preparation of a family of dinuclear monocyclopentadienyl imidoniobium and -tantalum complexes was achieved by two different synthetic routes. The diimido complexes [{M(Cp′)Cl2}2(μ-1,i-NC6H4N)] [Cp′ = η5-C5H4SiMe3, M = Nb, i = 4 (1); Cp′ = η5-C5H4SiMe3, M = Nb, i = 3 (2); Cp′ = η5-C5H4SiMe3, M = Nb, i = 2 (3); Cp′ = η5-C5Me5, M = Nb, i = 4 (4); Cp′ = η5-C5Me5, M = Nb, i = 3 (5); Cp′ = η5-C5H4SiMe3, M = Ta, i = 4 (6); Cp′ = η5-C5H4SiMe3, M = Ta, i = 3 (7)] were prepared by the reaction of one equivalent of the trichloro precursor [{MCl3}2(μ-1,i-NC6H4N)] (M = Nb, Ta, i = 4, 3 or 2) with two equivalents of either C5H4(SiMe3)2 or C5Me5(SiMe3). Complexes 1−7 can also be prepared by the react…
Synthesis and reactivity of new mono- and dinuclear niobium and tantalum imido complexes: X-ray crystal structure of [Ta(η5-C5H4SiMe3)Cl2{NC6Me4-4-(N(SiMe3)2)}]
Abstract The reaction of [1,4-{SiMe3(H)N}2C6Me4] (1) with 2 equivalents of LiBun followed by the addition of SiMe3Cl gave the diamine compound [1,4-{(SiMe3)2N}2C6Me4] (2). [Ta(η5-C5H4SiMe3)Cl4] reacts with 2, in a 2:1 stoichiometric ratio, to initially yield a mixture of the dinuclear, [{Ta(η5-C5H4SiMe3)Cl2}2(μ-1,4-NC6Me4N)] (3), and mononuclear, [Ta(η5-C5H4SiMe3)Cl2{ NC6Me4-4-(N(SiMe3)2)}] (4), imido complexes. 3 can be obtained exclusively by submitting the reaction mixture to repeated cycles of evacuation, to remove volatiles, followed by addition of solvent and subsequent heating. The mononuclear imido complex 4 was isolated from the reaction of [Ta(η5-C5H4SiMe3)Cl4] with 2 in a 1:1 sto…