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Synthesis and reactivity of mixed-ring indenyl complexes of molybdenocene |
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| Authors: | Isabel S Gonçalves Cláudia CL Pereira |
| Institution: | a Department of Chemistry, CICECO, University of Aveiro, Campus de Santiago, 3810-193 Aveiro, Portugal b Instituto de Tecnologia Química e Biológica da Universidade Nova de Lisboa, Quinta do Marquês, EAN, Apt. 127, 2781-901 Oeiras, Portugal c Escola Superior de Tecnologia, Instituto Politécnico de Setúbal, 2910-761 Setúbal, Portugal |
| Abstract: | The complex IndCpMo(NCMe)2]BF4]2 provides a suitable entry to the synthesis of IndCpMoBr2 and IndCpMoMe2. The latter, also available from IndCpMoX2 (X = Cl, Br) and MeMgCl, reacts with HCl to give IndCpMoCl(Me) which, in turn reacts with NaSPh to yield IndCpMo(SPh)(Me). Cyclic voltammetry shows that these three alkyl complexes undergo a 1e reversible oxidation to 17 e MoV cations. IndCpMoCl(Me) is oxidized by Cp2Fe]BF4 to afford IndCpMoCl(Me)]BF4 in 95% yield. Reaction of IndCpMo(NCMe)2]BF4]2 with KBPz4 in CH2Cl2/NMF leads to IndCpMo(κ2-BPz4)]BF4. Taken together with previous reports these results show that the indenyl ring slows down substitutional chemistry at the  fragment (Cp′ = Cp, Ind) by steric reasons, overshadowing any acceleration due to a possible indenyl effect. |
| Keywords: | Molybdenum Cyclopentadienyl Indenyl Molybdenocene Mixed-ring indenyl complexes |
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