DUGi

Ruthenium Complexes with Chiral Bis-Pinene Ligands: an Array of Subtle Structural Diversity

http://dugi.udg.edu/item/http:@@@@hdl.handle.net@@2072@@294970

A new chiral derivative of the N,N-bis(2-pyridylmethyl)ethylamine (bpea) ligand, Me-pinene[5,6]bpea [(-)-L1], has been prepared from a new aldehyde building block [Me-pinene-aldehyde, (-)-4] arising from the monoterpene chiral pool. The tridentate (-)-L1 ligand has been employed to prepare a new set of Ru-Cl complexes in combination with didentate 2,2’-bipyridine (bpy) with the general formula [RuCl((-)-L1)(bpy)](+). These complexes have been characterized in solution by cyclic voltammetry, UV-vis, and 1D and 2D NMR spectroscopy. Isomeric mixtures of trans,fac-C1a and anti,mer-C1c compounds are formed when (-)-L1 is reacted with a [Ru(bpy)(MeOH)Cl-3] precursor. Density functional theory calculations of all of the potential isomers of this reaction have been performed in order to interpret the experimental results in terms of electronic and steric effects and also to unravel the observed isomerization pathway between anti,mer-C1c and trans,fac-C1a

Support from MINECO (Grants CTQ2011-26440, CTQ2010-21497, and CTQ2011-23156/BQU) is gratefully acknowledged. Financial help from the DIUE of the Generalitat de Catalunya (Projects 2009SGR637and XRQTC) and the FEDER fund (European Fund for Regional Development) for Grant UNGI08-4E-003 is acknowledged. L.V. is grateful for the award of a FI doctoral grant from AGAUR. A.P. is grateful to the European Commission (Grant CIG09-GA-2011-293900), Spanish MICINN (Ramon y Cajal Contract RYC-2009-05226), and Generalitat de Catalunya (Grant 2011BE100793). Support for the research of M.S. was received through the ICREA Academia 2009 prize for excellence in research funded by the DIUE of the Generalitat de Catalunya

American Chemical Society