The unprecedented bridging coordination mode of 1,1-cyclobutane dicarboxylate (mu-cbdc-O,O') stabilized by intramolecular hydrogen bonds in ruthenium(II) complexes.
The 1,1-cyclobutane dicarboxylate ligand (cbdc), that normally binds to metal centres as a chelate (eta(2)-cbdc-O,O'), prefers to bind in an unprecedented bridging fashion (micro-cbdc-O,O') on cationic Ru(ii) centres bearing ancillary ligands (e.g. H(2)O, NH(3)) 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-[RuCl(2)(dmso-S)(3)(dmso-O)]() and cbdc in a number of different reaction conditions is the dinuclear species with two bridging cbdc units fac-[Ru(micro-cbdc-O,O')(dmso-S)(3)(H(2)O)](2) (2). Similarly, reaction of cis,fac-[RuCl(2)(dmso-S)(3)(NH(3))] (3) with cbdc yielded the corresponding dinuclear species fac-[Ru(micro-cbdc-O,O')(dmso-S)(3)(NH(3))](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 H(2)O or NH(3) 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(eta(2)-cbdc-O,O')(dmso-S)(3)]}(5), was isolated under appropriate conditions form the reaction of 1 with K(2)(cbdc) and was demonstrated to be an intermediate in the formation of 2.
Bratsos
Ioannis
I
Institute of Physical Chemistry, NCSR Demokritos, 15310 Ag. Paraskevi, Athens, Greece. bratsos@chem.demokritos.gr
Zangrando
Ennio
E
Serli
Barbara
B
Katsaros
Nikos
N
Alessio
Enzo
E
D018360:Crystallography, X-Ray / Q000379:methods; D003503:Cyclobutanes / Q000737:chemistry*; D003998:Dicarboxylic Acids / Q000737:chemistry*; D006860:Hydrogen Bonding; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D012428:Ruthenium / Q000737:chemistry*; D013055:Spectrophotometry, Infrared / Q000379:methods
C509875:1,1-cyclobutane dicarboxylate; D003503:Cyclobutanes; D003998:Dicarboxylic Acids; D008024:Ligands; D009942:Organometallic Compounds; D012428:Ruthenium