Abstract
Enantiomerically pure, chiral terpyridyl-type ligands L1 (‘dipineno’-[5,6∶5″,6″]-fused 2,2′∶6′,2″-terpyridine) and L2 (‘dipineno’-[4,5∶4″,5″]-fused 2,2′∶6′,2″-terpyridine) have been synthesized in high yields starting from 2,6-diacetylpyridine and enantiopure α-pinene. Complexes of L1 and L2 with RhIII and RuII have been prepared and studied spectroscopically. The complexes [Ru(L)2][PF6]2 (L = L1 or L2) were obtained in high yields using microwave heating in ethylene glycol as solvent. The rhodium(III) and ruthenium(II) complexes of L1 and L2 have a helically distorted terpyridyl moiety, as shown by the considerable optical activity in the ligand centered and metal to ligand charge transfer transitions. Crystal structures of [Rh(L1)Cl3] and [Ru(L1)Cl3] show a considerable out of plane distortion of the terpyridyl moiety, whereas free L2 and [Ru(trpy)(L2)][PF6]2 have a more planar arrangement of the pyridyl units.
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