Unexpected Formation of Ferrocenyl(vinyl)benzoquinoline Ligands by Oxidation of an Alkyne Benzoquinolate Platinum(II) Complex
作者:Jesús R. Berenguer、Julio Fernández、Nora Giménez、Elena Lalinde、M. Teresa Moreno、Sergio Sánchez
DOI:10.1021/om4004384
日期:2013.7.22
Oxidation of [Pt(bzq-kappa N,kappa C-10)(C6F5)(eta(2)-HC CFc)] (1) with PhICl2 and I-2 affords the unusual halideferrocenyl(vinyl)benzoquinoline Pt-II derivatives [Ptbzq-kappa N-eta(2)-CH=C(X)Fc}(C6F5)X] (X = Cl (4a), I (4b)), arising from C-X and C-C coupling processes, together with small amounts of the corresponding Pt-IV products [Pt(bzq-kappa N,kappa C-10)(C6F5)X(mu-X)}(2)] (X = Cl (5a), I (5b), respectively. Complexes 4 are very stable but they undergo easy displacement reactions with PPh3, yielding trans-[Pt(C6F5)X(PPh3)(2)] and the corresponding new functionalized (vinyl)-benzoquinoline ligands [(Z)-bzq-CH=C(X)Fc] (X = Cl (6a), I (6b)). The dinuclear Pt-IV derivatives 5 are alternatively obtained in high yield by oxidation of the solvate [Pt(bzq-kappa N,kappa C-10)(C6F5)(CH3COCH3)] (2). Treatment of 5 with dmso or direct oxidation of [Pt(bzq-kappa N,kappa C-10)(C6F5)(tht)] (3) provides mononuclear [Pt(bzq-kappa N,kappa C-10)(C6F5)X-2(L)] (L = dmso (7a-c), tht (8a-c)) as a mixture of cis and trans isomers.