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Issue 45, 2017
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Synthesis of 13-vertex dimetallacarboranes by electrophilic insertion into 12-vertex ruthenacarboranes

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Abstract

The electrophilic insertion of organometallic species into metallacarboranes was studied in detail for the model compound – the 12-vertex closo-ruthenacarborane anion [Cp*Ru(C2B9H11)] (1). Reactions of the anion 1 with the 12-electron cationic species [M(ring)]+ (M(ring) = RuCp, RuCp* and Co(C4Me4)) gave the 13-vertex closo-dimetallacarboranes Cp*Ru(C2B9H11)M(ring). Similar reactions of the neutral ruthenacarborane Cp*Ru(Me2S-C2B9H10) produce the cationic dimetallacarboranes [Cp*Ru(Me2S-C2B9H10)M(ring)]+. The symmetrical 13-vertex diruthenacarboranes (C5R5)Ru(R2C2B9H9)Ru(C5R5) can be prepared by the direct reactions of Tl2[7,8-R2-7,8-C2B9H9] (R = H and Me) with two equivalents of [CpRu(MeCN)3]+ or [Cp*RuCl]4. The insertions of the 14-electron cationic species [M(ring)]+ (M(ring) = NiCp, NiCp* and Co(C6Me6)) into 1 gave the 13-vertex dimetallacarboranes Cp*Ru(C2B9H11)M(ring), which have a distorted framework with one open face. The structures of Cp*Ru(C2B9H11)Co(C4Me4) and Cp*Ru(C2B9H11)NiCp were established by X-ray diffraction. Some of the 13-vertex dimetallacarboranes have two electrons less than required by Wade's rules. This violation is explained by the absence of the appropriate pathway for the distortion of the framework.

Graphical abstract: Synthesis of 13-vertex dimetallacarboranes by electrophilic insertion into 12-vertex ruthenacarboranes

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Publication details

The article was received on 18 Sep 2017, accepted on 13 Oct 2017 and first published on 16 Oct 2017


Article type: Paper
DOI: 10.1039/C7DT03504G
Citation: Dalton Trans., 2017,46, 15710-15718
  • Open access: Creative Commons BY license
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    Synthesis of 13-vertex dimetallacarboranes by electrophilic insertion into 12-vertex ruthenacarboranes

    D. S. Perekalin, K. A. Lyssenko, A. R. Kudinov, M. Corsini and F. Fabrizi de Biani, Dalton Trans., 2017, 46, 15710
    DOI: 10.1039/C7DT03504G

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