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Issue 13, 2014
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Base-mediated transformation of the agostic (π-allyl)-closo-rhodacarboranes into complexes with an open (1-5-η5)-pentadienyl ligand

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Abstract

The reactions of agostic (CH3⋯Rh) complexes [3-{(1-3-η3)-1,1,2-trimethylallyl}-1-R-2-R′-closo-3,1,2-RhC2B9H9] [1: R = R′ = Me; 2: R,R′ = μ-(ortho-xylylene); 3: R = Ph, R′ = Me] in a cooled (+5 °C) toluene solution with the strong non-nucleophilic base N,N,N′,N′-tetramethylnaphthalene-1,8-diamine (tmnd) formally involve a linear coupling of the π-allyl ligand of one molecule of the complex to the π-allyl ligand of the second molecule of the complex, ultimately forming the structurally novel mononuclear species [3-{(1-5-η5)-2,3-dimethyl-5-(3-methylbuten-2-yl)pentadienyl}-1-R-2-R′-closo-3,1,2-RhC2B9H9] (4, 5) and (6a,b, a mixture of diastereomers). Complexes 5 and 6a,b were also prepared using weaker bases such as PPh3 or even EtOH instead of tmnd. All new complexes 4–6 were characterized by a combination of analytical and multinuclear NMR data, as well as by single-crystal X-ray diffraction studies of two selected species 5 and the major diastereomer of 6, which revealed an open η5-pentadienyl coordination mode of the hydrocarbon ligands in these complexes.

Graphical abstract: Base-mediated transformation of the agostic (π-allyl)-closo-rhodacarboranes into complexes with an open (1-5-η5)-pentadienyl ligand

  • This article is part of the themed collection: Carboranes
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Article information


Submitted
09 Oct 2013
Accepted
04 Dec 2013
First published
06 Jan 2014

Dalton Trans., 2014,43, 5076-5082
Article type
Paper

Base-mediated transformation of the agostic (π-allyl)-closo-rhodacarboranes into complexes with an open (1-5-η5)-pentadienyl ligand

K. I. Galkin, F. M. Dolgushin, A. F. Smol'yakov, E. A. Sergeeva, I. A. Godovikov and I. T. Chizhevsky, Dalton Trans., 2014, 43, 5076
DOI: 10.1039/C3DT52838C

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