Issue 27, 2010

Intramolecular electron transfer in cyanide bridged adducts comprising RuII/RuIII tetracarboxylate and [MnI(CO)(CN)(tBuNC)4] units

Abstract

Reaction of mixed valence ruthenium tetracarboxylates [Ru2II,III(R1COO)2(R2COO)2Cl] (R1 = Me, R2 = 2,4,6-iPr-Ph or R1 = R2 = tBu) with two equivalents of the octahedral manganese complex [MnI(CO)(CN)(tBuNC)4] leads to the formation of cyanide bridged heteronuclear coordination compounds of the general formula {[Ru2II,III(R1COO)2(R2COO)2][MnI(CO)(CN)(tBuNC)4]2}Cl. In solution an intramolecular electron transfer from manganese towards the multiply bonded Ru2 core occurs that is verified by EPR and IR spectroscopy, magnetic measurements and DFT calculations. Nevertheless, disproportionation of an initially formed {MnI–Ru2II,III–MnI}+ adduct into {MnII–Ru2II,III–MnI}2+ and {MnIRu2II,IIMnI} species cannot be completely ruled out.

Graphical abstract: Intramolecular electron transfer in cyanide bridged adducts comprising RuII/RuIII tetracarboxylate and [MnI(CO)(CN)(tBuNC)4] units

Supplementary files

Article information

Article type
Paper
Submitted
10 Nov 2009
Accepted
06 May 2010
First published
02 Jun 2010

Dalton Trans., 2010,39, 6249-6254

Intramolecular electron transfer in cyanide bridged adducts comprising RuII/RuIII tetracarboxylate and [MnI(CO)(CN)(tBuNC)4] units

W. Imhof, A. Sterzik, S. Krieck, M. Schwierz, T. Hoffeld, E. T. Spielberg, W. Plass and N. Patmore, Dalton Trans., 2010, 39, 6249 DOI: 10.1039/B923536A

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