Chemistry of Diruthenium Analogue of Pentaborane(9) With Heterocumulenes: Toward Novel Trimetallic Cubane-Type Clusters
Résumé
Reactions of the CS2 and CO2 heterocumulene ligands with nido-ruthenaborane cluster [1,2-(Cp*Ru)2(μ-H)2B3H7], 1, were explored. Compd. 1 when treated with CS2 underwent metal-assisted hydroboration to yield arachno-ruthenaborane [(Cp*Ru)2(B3H8)(CS2H)], 2, with a dithioformato ligand attached to it. The chem. of 2 was then explored with various transition metal carbonyl compds. under photolytic and thermolytic conditions. Thermolysis of 2 with [Mn2(CO)10] gave an unprecedented cubane-type cluster [(Cp*Ru)2Mn(CO)3(CS2H2)B3H4], 3, with a rare [M3E5] formulation (E = B, S). However, when compd. 2 was photolyzed in the presence of [Mn2(CO)10], it yielded an incomplete cubane-type cluster [(Cp*Ru)2Mn(CO)3BH2(CS2H2)], 4. The room-temp. reaction of 2 with [Fe2(CO)9] yielded heterometallic arachno clusters [(Cp*Ru)(CO)2{Fe(CO)3}2S2CH3], 6 and [(Cp*Ru)2(B3H8)(CO){Fe(CO)3}2(CS2H)], 7. In contrast, photolysis of 2 with [Fe2(CO)9] yielded a tetrahedral cluster [(Cp*Ru)(CO)2S(μ-H){Fe(CO)3}3], 8, tethered to an exo-polyhedral moiety [(Cp*Ru)(CO)2]. Compd. 6 provides an unusual bonding pattern by fusing the wing-tip vertex (S) of the [Fe2S2] butterfly core by an exo-polyhedral [(Cp*Ru)(CO)2] unit. D. functional theory calcns. were carried out to provide insight into the mechanistic pathway, electronic structure, and bonding properties.