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Issue 30, 2009
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Synthesis and reactivity of a Ru(I) dimer devoid of π-acid ligands

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Zinc reduction of [(Cym)RuCl2]2 gives [(Cym)RuCl]2, (Cym = 1,4-MeiPrC6H4), whose reactivity is evaluated. This RuI dimer with two bridging chlorides shows no reactivity towards H2, N2, N2O or methyl triflate, but does add HCl to form (Cym)2Ru2HCl3. Attempts to form a monomeric monovalent ruthenium complex with dppm, Ph2PCH2PPh2, gives disproportionation to (Cym)RuCl21-dppm) and (Cym)Ru(η2-dppm). With terpyridyl, the analogous disproportionation behavior is observed, to form Ru(terpy)22+ and a zero valent product, which decomposed before it could be isolated. The molecular orbitals, from a DFT calculation, of [(Cym)RuCl]2 show the LUMO to be in a sterically crowded region of the molecule, and thus helps to account for the reactivity targeted for small and more nucleophilic reagents, while the HOMO is accessible to reaction with HCl.

Graphical abstract: Synthesis and reactivity of a Ru(i) dimer devoid of π-acid ligands

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Publication details

The article was received on 10 Feb 2009, accepted on 11 May 2009 and first published on 19 Jun 2009

Article type: Paper
DOI: 10.1039/B902759A
Citation: Dalton Trans., 2009,0, 6001-6006

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    Synthesis and reactivity of a Ru(I) dimer devoid of π-acid ligands

    A. G. Walstrom, M. Pink, X. Yang and K. G. Caulton, Dalton Trans., 2009, 0, 6001
    DOI: 10.1039/B902759A

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