Synthesis, Crystal-Structure and Reactivity of (Mu-3-Eta-2-7-Oxabicyclo[2.2.1]Hept-5-Yn-2-One)-Nonacarbonyldihydridotri Ruthenium and (Mu-3-Eta-2-7-Oxabicyclo[2.2.1]Hept-5-Yn-2-One)-Hexacarbonyldihydridotri S(Triphenylphosphine)Triruthenium
The thermal reaction Of Ru3(CO)12 with (+/-) 7-oxabicyclo[2.2.1]hept-5-en-2-one (+/-)-2, (+/-) 7-oxabicyclo[2.2.1]hept-5-en-2-endo-ol 21 and the corresponding benzoate 22 afforded the [Ru3H2(CO)9 (7-oxabicyclo[2.2.1]hept-5-yn-2-yl)] clusters 13, 19 and 20, respectively. Treatment of 13, 19 and 20 with triphenylphosphine and Me3NO led to the corresponding Ru3H2(CO)6 (Ph3P)3 (mu3-eta2-7-oxabicyclo[2.2.1]hept-5-yn-2-yl) complexes 17, 23 and 24, respectively, in which each of the ruthenium metallic centres bears one Ph3P ligand. Single crystal diffraction studies of di(mu-hydrido)(7-oxabicyclo[2.2.1]hept-5-yn-2-one)-triangulo-tris(tricar bonylruthenium)(3Ru-Ru) 13 and of di(mu-hydrido) (7-oxabicyclo[2.2.1]hept-5-yn-2-one)-triangulo-tris[dicarbonyl(triphenyl phosphine]ruthenium)(3Ru-Ru) 17 are reported. Preliminary studies on the reactivity of these new clusters are described; treatment of the complex 20 derived from 7-oxabicyclo[2.2.1]hept-5-en-2-endo-yl benzoate with (CH3)3SiOSO2CF3 gave a mixture of [RU3H2(CO)9(benzyne)] 25 and [RU3H2(CO)9(C6H3-OCO-C6H5)] 26.
Keywords: Ruthenium clusters ; metal complexes of ; 7-oxabicyclo[2.2.1]hept-5-yn-2-yl derivatives ; c-h insertion of ; ru3(co)12 ; lateral control ; ru3h2(co)9(didehydrobenzene) ; ru3h2(co)9(didehydrophenyl benzoate ; carbonyltriphenylphosphine ligand ; exchange ; ruthenium induced conversion of ; 7-oxabicyclo[2.2.1]hept-5-en-2-one into catechol ; Pure 7-oxabicyclo<2.2.1>hept-5-en-2-yl derivatives ; metal-carbonyls ; dissociative chemisorption ; cyclo-dimerization ; co substitution ; naked ; sugars ; dodecacarbonyltriruthenium ; complexes ; kinetics ; 5 ; 6-dimethylidene-7-oxabicyclo<2.2.1>hept-2-ene
Univ lausanne,chim sect,2 rue barre,ch-1005 lausanne,switzerland. univ toledo,dept chem,toledo,oh 43606.
Record created on 2005-11-09, modified on 2016-08-08