Reactivity of 2-(2-hydroxyphenyl) benzoxazole and 2-(2-hydroxyphenyl) benzothiazole towards group 10 transition metals. Evaluation in palladium catalyzed Suzuki-Miyaura C-C couplings

摘要

A series of group 10 transition metal complexes based on 2-(2-hydroxyphenyl) benzoxazole (HPBO) and 2-(2-hydroxyphenyl) benzothiazole (HPBT) have been prepared. Reactions of nickel or palladium acetates with HPBT and HPBO produce chelate N-O coordinated compounds respectively. Whilst reaction of [k(2)PtCl(4)] with HPBT affords organometallic species product of a C-H bond activation of the phenolic moiety at room temperature. The molecular structures of the three complexes were unambiguously determined by means of single crystal X-ray diffraction analyses. The nickel compound [{Ni(k(2)-N,O-HPBT)} 2(mu(2)-O-HPBT)(2)(mu(2)-OOCCH3)] (1) showing to be binuclear with the nickel ions found in six-coordinated distorted octahedral environments. Conversely, compound [Pd(k(2)-N, O-HPBO)(2)] (2) is a tetracoordinated monomer with the Pd center having a slightly distorted square planar geometry. Similarly, platinacycle [Pt(k(1)-N-HPBT)(k(2)-N, C-HPBT)Cl] (3) shows the Pt center into a slightly distorted square planar geometry, exhibiting ligand HPBT in two different coordination modes, as single k(1)-N coordinated and as k(2)-N-C metalated chelate bidentate ligand, completing the coordination sphere with a chloride ligand. The catalytic activity of the palladium complex (2) was evaluated in Suzuki-Miyaura cross couplings, showing good activity. (C) 2015 Elsevier B.V. All rights reserved.