Synthesis and reactivity of mixed-ring indenyl complexes of molybdenocene

abstract

The complex [IndCpMo(NCMe)(2)][BF4](2) provides a suitable entry to the synthesis of IndCpMoBr(2) and IndCpMoMe(2). The latter, also available from IndCpMoX(2) (X = Cl, Br) and MeMgCl, reacts with HCl to give IndCpMoCI(Me) which, in turn reacts with NaSPh to yield IndCpMo(SPh)(Me). Cyclic voltammetry shows that these three alkyl complexes undergo a le reversible oxidation to 17 e Mo-V cations. IndCpMoCl(Me) is oxidized by [Cp2Fe]BF4 to afford [IndCpMoCl(Me)]BF4 in 95% yield. Reaction of [IndCpMo(NCMe)(2)][BF4](2) with KBPz(4) in CH2Cl2/NMF leads to [IndCpMo(kappa(2) -BPz(4))]BF4. Taken together with previous reports these results show that the indenyl ring slows down substitutional chemistry at the Cp'Mo-2(IV) fragment (Cp' = Cp, Ind) by steric reasons, overshadowing any acceleration due to a possible indenyl effect. (c) 2005 Elsevier B.V. All rights reserved.

keywords

PI-CYCLOPENTADIENYL-MOLYBDENUM; BIS-INDENYL; TUNGSTEN COMPLEXES; HYDRIDE COMPLEXES; CRYSTAL-STRUCTURE; X-RAY; SLIPPAGE; ALKYL; DERIVATIVES; ANALOGS

subject category

Chemistry

authors

Goncalves, IS; Gamelas, CA; Pereira, CCL; Romao, CC

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