Evidence for a dinuclear mechanism in alkyne hydrogenations catalyzed by pyrazolate-bridged diiridium complexes
The products obtained from the sequential reaction of [Ir2(mu-H)(mu-Pz)2H3(NCCH3)(PiPr3)2] (1) with diphenylacetylene and their subsequent reactions with hydrogen have been investigated in order to deduce the mechanisms operating in the hydrogenation reactions catalyzed by 1. The reaction of 1 with an excess of diphenylacetylene gives cis-stilbene and [Ir2(mu-H)(mu-Pz)2-[eta1-C6H4-2-[eta1-(Z)-C=CHPh]]((Z)-C(Ph) =CHPh](NCCH3)(PiPr3)2] (2), the structure of which has been determined by X-ray diffraction. The formation of 2 involves the intermediate species [Ir2(mu-H)(mu-Pz)2H2((Z)-C(Ph)=CHPh](NCCH3)-(PiPr3)2](3),[Ir2(mu-H)(mu-Pz)2H[(Z)-C(Ph)=CHPh]2(NCCH3)(PiPr3)2] (4), and [Ir2(mu-H)(mu-Pz)2H[eta1-C6H4-2-[eta1-(Z)-C=CHPh](NCCH3)(PiPr3)2] (5), which have been isolated and characterized. These three complexes react with hydrogen to give cis-stilbene and 1 and are possible intermediates of the diphenylacetylene hydrogenation under catalytic conditions. Nevertheless, the rate of formation of 5 is very slow compared with the rate of catalytic hydrogenation, which excludes its participation during catalysis. Compound 2 also reacts with hydrogen in benzene, but in this case the hydrogenation gives 1,2-diphenylethane as the sole organic product. The course of this reaction in acetone has been investigated, and deuteration experiments were carried out. The formation of [Ir2(mu-H)(mu-Pz)2H[eta1-C6H4-2-[eta1-(Z)-C=CHPh]](OC(CD3)2)(PiPr3)2] (6) and [Ir2(mu-H)(mu-Pz)2H[eta1-C6H4-2-[eta1-(Z)-C-CHPh]](NCCH3)(PiPr3)2] (7) was observed under these conditions. The experimental evidence obtained supports two alternative mechanisms for the alkyne hydrogenation catalyzed by 1, one of them being dinuclear and the other mononuclear. The experimental data suggest that the former is favored.
Departamento de Quimica Inorganica, Instituto de Ciencia de Materiales de Aragon, Universidad de Zaragoza-CSIC, Spain.
F
Torres
E
Sola
A
Elduque
AP
Martinez
FJ
Lahoz
LA
Oro