44 Synthesis and Characterization of Ru2(L)3(ac)Cl and Ru2(L)3(ac)(CN)2, Where L =2-(2,4,6-trimethylanilino)Pyridinate Ligand and Ac = Acetate

Wednesday, November 4, 2009
Ballroom A+B (Camino Real Hotel)
Magnus U. Legemah, Graduate student , Department of Chemistry, University of Houston, Houston, TX
John L. Bear , Department of Chemistry, University of Houston, Houston, TX
Eric Van Caemelbecke , Houston Baptist University, Houston, TX
Karl M. Kadish , Department of Chemistry, University of Houston, Houston, TX

The  reaction of  Ru2(ac)4Cl ( ac = acetate) with  excess ap or substituted ap  ( ap = anilinopyridinate) in a melt under a stream of nitrogen  results in displacement of  all four acetate groups  by the bridging ligand to form Ru2(ap)4Cl. However, when  2,4,6-(CH3)3ap was used in place of ap, the only isolated product was  Ru2[2,4,6-(CH3) 3ap]3(ac)Cl, as confirmed by an X-ray crystal structure. This compound was characterized by spectroscopic and electrochemical methods. Ru2[2,4,6-(CH3)3ap]3(ac)Cl in CH2Cl2 / TBAP (TBAP = tetrabutylammonium perchlorate), exhibits one oxidation  at  E1/2 =  0.47 V and one reduction at E1/2 = -0.77 V assigned as Ru25+/6+ and Ru25+/4+, respectively. Ru2[2,4,6-(CH3)3ap]3(ac)Cl also reacts with CN- to form Ru2[2,4,6-(CH3)3ap]3(ac)(CN)2 (which has a Ru26+ core) in a methanol/ tetrahydrofuran mixture under aerobic conditions. Ru2[2,4,6-(CH3)3ap]3(ac)(CN)2 was also characterized by spectroscopic and electrochemical techniques. Ru2[2,4,6-(CH3)3ap]3(ac)(CN)2 undergoes a reversible  Ru26+/5+ reduction  at E1/2 = -0.32 V and an  irreversible Ru25+/4+ reduction at Ep = -1.26 V in CH2Cl2 / TBAP.

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