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Published on: October 3, 2014
Synthesis and Characterization of the First Cyclic Monothioether Derivative of 1,2-o-Carborane and Its Reactivity
Clara Viñas1, M. Rosa Cirera, Francesc Teixidor
1Institut de Ciència de Materials de Barcelona (CSIC), Campus UAB, E-08193 Bellaterra, Spain, Sociedad Española de Carburos Metálicos, S.A. Passeig de la Zona Franca, 14-20. 08038 Barcelona, Spain, Department of Chemistry, University of Helsinki, Box 55, FIN 00014 Helsinki, Finland, and Department of Chemistry, University of Turku, FIN 20014 Turku, Finland.
Abstract:
The first cyclic monothioether derivative of [C(2)B(9)H(12)](-) has been synthesized from 1-(SH)-1,2-C(2)B(10)H(11). Reaction of the latter with (n)BuLi and 1,3-dibromopropane leads to 1,2-&mgr;-(S(CH(2))(3))-1,2-C(2)B(10)H(10). Partial degradation leads to [7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10)](-). Reaction of [7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10)](-) with [PdCl(2)(PRR'(2))(2)] leads to different sets of compounds depending on the nature of R and R'. If R = R' = (t)Bu, a closo compound with one vertex occupied by "[Pd(P(t)Bu(3))(2)]" is obtained. When aryl groups are present in the starting phosphine complex, the zwitterionic non-metal-containing compounds are obtained. The crystal structure of one of them has been determined, and the compound has been proven to be 7,8-&mgr;-(S(CH(2))(3))-11-PPh(3)-7,8-C(2)B(9)H(9). The reaction of [7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10)](-) with [RhCl(PPh(3))(3)] leads to [Rh(7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10))(PPh(3))(2)]. An agostic B-Hright harpoon-up Rh interaction has been produced, identified by a (1)H{(11)B} NMR resonance at -4.78 ppm. In this instance the cluster is connected to "Rh" via the thioether and B(11)-H. The reaction of [7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10)](-) with [RuCl(2)(PPh(3))(3)] leads to a compound with two B-Hright harpoon-up Ru interactions. Contrarily to its noncyclic analogues, it seems that only one isomer has been obtained.
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