Issue 24, 2005
From the journal:

Dalton Transactions

The unprecedented bridging coordination mode of 1,1-cyclobutane dicarboxylate (μ-cbdc-O,O′) stabilized by intramolecular hydrogen bonds in ruthenium(ii) complexes†

Ioannis Bratsos,a   Ennio Zangrando,b   Barbara Serli,b   Nikos Katsarosa  and  Enzo Alessio*b  

* Corresponding authors

a Institute of Physical Chemistry, NCSR “Demokritos”, 15310 Ag. Paraskevi, Athens, Greece
E-mail: bratsos@chem.demokritos.gr
Fax: +30 210 6511766
Tel: +30 210 6503624

b Dipartimento di Scienze Chimiche, Università di Trieste, Via L. Giorgieri 1, Trieste, Italy
E-mail: alessi@univ.trieste.it
Fax: +39 040 5583903
Tel: +39 040 5583961

Abstract

The 1,1-cyclobutane dicarboxylate ligand (cbdc), that normally binds to metal centres as a chelate (η2-cbdc-O,O′), prefers to bind in an unprecedented bridging fashion (μ-cbdc-O,O′) on cationic Ru(II) centres bearing ancillary ligands (e.g. H2O, NH3) capable of making intramolecular H-bonds with the non-coordinated oxygen atoms of the carboxylate groups. Thus, the thermodynamic product of the reaction between cis,fac-[RuCl2(dmso-S)3(dmso-O)] (1) and cbdc in a number of different reaction conditions is the dinuclear species with two bridging cbdc units fac-[Ru(μ-cbdc-O,O′)(dmso-S)3(H2O)]2 (2). Similarly, reaction of cis,fac-[RuCl2(dmso-S)3(NH3)] (3) with cbdc yielded the corresponding dinuclear species fac-[Ru(μ-cbdc-O,O′)(dmso-S)3(NH3)]2 (4), in which ammonia occupies the position of the water molecule in 2. Both dinuclear species 2 and 4 were characterized by X-ray crystallography and have an anti geometry with respect to the H2O or NH3 ligands. The results from the X-ray studies are consistent with the NMR spectroscopic data, indicating that the dinuclear structures observed in the solid state are maintained in solution. The mononuclear anionic complex with a chelating cbdc unit, K{fac-[RuCl(η2-cbdc-O,O′)(dmso-S)3]} (5), was isolated under appropriate conditions form the reaction of 1 with K2(cbdc) and was demonstrated to be an intermediate in the formation of 2.

Graphical abstract: The unprecedented bridging coordination mode of 1,1-cyclobutane dicarboxylate (μ-cbdc-O,O′) stabilized by intramolecular hydrogen bonds in ruthenium(ii) complexes

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Article information

DOI
https://doi.org/10.1039/B503412D
Article type
Paper
Submitted
08 Mar 2005
Accepted
20 May 2005
First published
03 Oct 2005

Dalton Trans., 2005, 3881-3885

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The unprecedented bridging coordination mode of 1,1-cyclobutane dicarboxylate (μ-cbdc-O,O′) stabilized by intramolecular hydrogen bonds in ruthenium(II) complexes

I. Bratsos, E. Zangrando, B. Serli, N. Katsaros and E. Alessio, Dalton Trans., 2005, 3881 DOI: 10.1039/B503412D

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