Issue 2, 2002
From the journal:

Journal of the Chemical Society, Dalton Transactions

The chemistry of ruthenium complexes of 1,2-dicyanoethylene dithiolate (mnt2−). Synthesis and characterization of [RuIV/III(mnt)3]2−/3− and the derivatives trans-[RuIII(mnt)2(PPh3)2]−, trans-[RuIII(mnt)2(py)2]− and trans-[RuIV(mnt)2(Br)2]2−

Rabindranath Maiti,a   Maoyu Shanga  and  A. Graham Lappin*a  

* Corresponding authors

a University of Notre Dame, Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, Notre Dame, IN 46556-5670, USA

Abstract

The chemistry of ruthenium(III) and ruthenium(IV) complexes with 1,2-dicyanoethylene dithiolate(2−) (mnt2−) as ligand has been investigated. The tris-complex [RuIII(mnt)3]3− is readily prepared and oxidized to [RuIV(mnt)3]2−. Both complex anions are characterized by X-ray structural analysis. Ligand substitution behavior of the anions has been examined. Reactions of [RuIII(mnt)3]3− with triphenylphosphine and pyridine are sluggish while reactions of [RuIV(mnt)3]2− with these nucleophiles are complex, involving reduction by the displaced mnt2− ligand, to give trans-[RuIII(mnt)2(PPh3)2]− and trans-[RuIII(mnt)2(py)2]− respectively. A ruthenium(IV) complex, trans-[RuIV(mnt)2(Br)2]2−, is formed on treatment of [RuIV(mnt)3]2− with Br2. These three products have also been characterized by X-ray crystallography. In solution, the complexes trans-[RuIII(mnt)2(PPh3)2]− and trans-[RuIV(mnt)2(Br)2]2− both lose one axial ligand in rapidly established equilibria. The complex, [RuIV(mnt)3]2−, undergoes an unusual photochemical rearrangement in the presence of oxygen resulting in formation of [RuII(mnts)2]2− where mnts2− is a novel tridentate sulfur-bound ligand.

Graphical abstract: The chemistry of ruthenium complexes of 1,2-dicyanoethylene dithiolate (mnt2−). Synthesis and characterization of [RuIV/III(mnt)3]2−/3− and the derivatives trans-[RuIII(mnt)2(PPh3)2]−, trans-[RuIII(mnt)2(py)2]− and trans-[RuIV(mnt)2(Br)2]2−

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Article information

DOI
https://doi.org/10.1039/B100603G
Article type
Paper
Submitted
16 Jan 2001
Accepted
06 Nov 2001
First published
12 Dec 2001

J. Chem. Soc., Dalton Trans., 2002, 244-251

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The chemistry of ruthenium complexes of 1,2-dicyanoethylene dithiolate (mnt2−). Synthesis and characterization of [RuIV/III(mnt)3]2−/3− and the derivatives trans-[RuIII(mnt)2(PPh3)2]−, trans-[RuIII(mnt)2(py)2]− and trans-[RuIV(mnt)2(Br)2]2−

R. Maiti, M. Shang and A. G. Lappin, J. Chem. Soc., Dalton Trans., 2002, 244 DOI: 10.1039/B100603G

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