Abstract
The reactions of dilithium 1,2-diamidobenzene, [1,2-(HN)2C6H4]Li2 (L(1)H2)Li2, and dilithium 1,8-diamidonaphthalene, [1,8-(NH)2C10H6]Li2 (L(2)H2)Li2, with Cp2Ni and Cp2V have been used to obtain the new complexes (L(2)H2)2Ni{Li(THF)2}2 (3), (L(2)H2)3V{Li(THF)2}3 (4) and (L(1)H2)6Ni6·{[(L(1)H2)3(L(1)H)3Ni6Li(THF)](2-)·2[Li(THF)4](+)} (5), in which retention or oxidation of the initial metal(ii) centre is observed. Whereas 3 and 4 contain one transition metal ion within ion-paired structures, 5 has a complicated co-crystalline composition which contains octahedral Ni6-cages constructed from six square-planar (16e) Ni(II) centres.
Highlights
In contrast to ferrocene (Cp2Fe), in which the Cp–Fe interactions are predominantly covalent, the other first-row metallocenes are far more polar
Extensive synthetic studies involving a broad range of N, O- and C-based organic acids and nucleophiles have identified three main types of reactivity; (i) the deprotonation of organic acids (RH) by the anionic Cp ligands,[1] (ii) the addition of weaker nucleophiles (R−) to the transition metal centre (M) without displacement of the Cp ligands,[2] and (iii) nucleophilic displacement of the Cp− ligands by stronger heteroatomic and organometallic nucleophiles (R−).[3]
Some of our most recent studies have shown that the use of Cp2M (M = V, Cr, Mn, Ni) as metal precursors can lead to formally multiply-bonded transition metal compounds
Summary
In contrast to ferrocene (Cp2Fe), in which the Cp–Fe interactions are predominantly covalent, the other first-row metallocenes are far more polar. The potential for complicated redox behaviour of the dianion of 1,2-diaminobenzene, [1,2-(HN)2C6H4]2− (L1H2), had already been observed in a number of main group[4] and transition metal reactions.[5] For example, the reaction of dilithium 1,2-diamidobenzene, [1,2-(HN)2C6H4]Li2 (L1H2)Li2 with the SnII base Sn(NMe2)[2] is known to result in the formation of a mixed oxidation state SnII/SnIV complex.[4] With this behaviour in mind we have begun to explore the reactions of (L1H2)Li2 with metallocene.
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