Facile and Selective Synthetic Approach for Ruthenium Complexes Utilizing a Molecular Sieve Effect in the Supporting Ligand

Abstract

It is extremely important for synthetic chemists to control the structure of new compounds. We have constructed ruthenium-based mononuclear complexes with the tridentate 2,6-di(1,8-naphthyridin-2-yl)pyridine (dnp) ligand to investigate a new synthetic approach using a specific coordination space. The synthesis of a family of new ruthenium complexes containing both the dnp and triphenylphosphine (PPh 3 ) ligands,, has been described. All complexes have been spectroscopically characterized in solution, and the nitrile complexes have also been characterized in the solid state through single-crystal X-ray diffraction analysis. Dnp in the present complex system behaves like a "molecular sieve" in ligand replacement reactions. Both experimental data and density functional theory (DFT) calculations suggest that dnp plays a crucial role in the selectivity observed in this study. The results provide useful information toward elucidating this facile and selective synthetic approach to new transition metal complexes. OPEN ACCESSInorganics 2013, 1 33

Light Activated Release of Nitrile Ligands from trans-Ru(L)(PPh3)2(nitrile) Complexes

“…To date the CDS contains just one Ru complex, containing a heterocyclic N-coordinated ligand, a benzonitrile ligand, and two PPh 3 groups. 12 Neither the Ru−N nitrile nor C� N bond lengths show a variation associated with the tridentate ligand, the nitrile ligand, or a comparison between the monoand bimetallic complexes. This behavior is due to the poor mixing of the Ru(d) and nitrile (π) orbitals.…”

“…In all of the studied complexes, the central Ru atom adopts slightly distorted octahedral coordination with trans configuration of PPh 3 ligands. To date the CDS contains just one Ru complex, containing a heterocyclic N-coordinated ligand, a benzonitrile ligand, and two PPh 3 groups . Neither the Ru–N nitrile nor CN bond lengths show a variation associated with the tridentate ligand, the nitrile ligand, or a comparison between the mono- and bimetallic complexes.…”

Innovative Inorganic Synthesis

“…The successful synthesis of the various members of this lanthanide series has facilitated a study of how varying the size of the central metal impacts on the structure and reactivity of the methanediide complexes. Meanwhile, Dai Oyama and his team from Fukushima University utilise a phenomenon, which they term as a "Molecular Sieve Effect" in their report on the synthesis of a series of new ruthenium complexes containing the triphenylphosphine ligand [6]. They capitalise on the ability of the tridentate 2,6-di(1,8-naphthyridin-2-yl)pyridine (dnp) ligand not only to stabilise resulting ruthenium complexes but also to improve the stereospecificity of the reactions dramatically.…”