1. Synthesis, Characterization and Reactivity of a Series of Ruthenium Acetylide Complexes Jason F. Hill and Cliff J. Timpson Roger Williams University, One Old Ferry Road, Bristol, Rhode Island 02809 Abstract Metal complexes based on ruthenium have enjoyed considerable attention due to the ability to extensively manipulate both the electrochemical and the photophysical properties of the complexes by varying substituents on the ligands. Recently, we have become interested in producing metal complexes of the type trans-[ClRu(dppm) 2 CCPh-4-Y] where Y is -NO 2, -H, and -OCH 3 in order to quantify the influence the Y substituent has on the metal-based redox potential and it’s ability to labilize the trans- chloride ligand in the presence of Tl+ ion. Following modified procedures of McDonagh et al. for the synthesis of acetylide complexes, we have been able to synthesis trans-[ClRu(dppm) 2 CCPh-4-H] and trans-[ClRu(dppm) 2 CCPh-4- OCH 3 ] in good yield. Our efforts to synthesis, purify, and characterize these complexes, along with preliminary kinetic studies of the chloride abstraction reactions will be presented. Methods and Materials Ruthenium acetylide complexes were prepared following modified procedures of McDonagh et al. 5 Spectroscopic grade solvents (Aldrich) and reagents (Aldrich) were obtained commercially and used as supplied. All synthetic reactions were conducted under argon atmosphere and products purified by column chromatography using basic alumina (Aldrich) and eluting with dichloromethane. Rate reactions were carried out in a 100:1 molar ratio thallium ion to ruthenium acetylide complex and monitored via cyclic voltammetry using a Bio-Analytical Systems (BAS) CV-50W equipped with 2mm Pt disk working electrode and Pt wire auxiliary electrode. All cyclic voltammetric measurements were obtained in 0.1M TBAH/CH 3 CN at a scan rate of 200mV/s and reported verses a Ag + /AgCl reference electrode. UV-Vis spectra were collected on a Hewlett-Packard HP-8453 Diode Array spectrophotometer. Infrared data was collected on a Perkin-Elmer 1600 series FT-IR. Acknowledgments Financial support for travel form RWU Provost-Sponsored Student Scholarship Research Award Financial supports for chemical and lab supplies from RWU Committee for Undergraduate Research Mr. David Futoma (RWU adjunct faculty) for his time and help in lab Dr. Stephen O’Shea for his time and help running NMR data Mrs. Lyndsey Medeiros (RWU ‘06) for her assistance in lab RWU Facilities and Stockroom Personnel References 1. Balzani, V; Scandola, F. Supermolecular Photochemistry; Wiley, Chinchester, UK, 1991. 2. Fischetti, L; Gordon, M; Reardon, M; Timpson, C.J. “Impact of Substituents on the Metal-based Redox Potential for a Series of Complexes Based on trans-[Cl(pyridine) 4 Ru-L] + where L is a Para-substituted Derivative of Cyanobenzene” Poster at ACS Meeting Anaheim Spring 2004. 3. Kuber, A; Nandor, H; Hira, S; Petricko, R; Von Riesen, D; Timpson, C. J. “In-Situ Generation of Trans- [Ru(pyridine) 4 (L)(Solvent)] 2+ Obtained by Cl- Abstraction from trans-[Ru(pyridine) 4 (L)Cl] + ” Poster at ACS Meeting San Diego Spring 2001. 4. McGrady, J.E.; Lovell. T.; Stranger, R.;Humphrey, M.G. Organometallics 1997, 16, 4004. 5. McDonagh, A.M.; Deeble, G.J.; Hurst, S.; Cifuentes, M.P.; Humphrey, M.G. J Chem. Ed. 2001, 78, 232. 6. Carol, F.A. Perspectives on Structure and Mechanism in Organic Chemistry. First ed. Brooks Cole: 1997: 384. Introduction Our group has been interested in exploring metal complexes of ruthenium where a halide ligand is formally trans to a ligand which may be synthetically altered to prepare oligomeric metal complexes. 1-3 Previous efforts in our group have explored the possibility of removing the halide in the complex [Ru(pyridine) 4 (L)Cl] + (where L is cyano benzene, n-cyano alkanes, and substituted pyridine derivatives.) via Tl+ or Ag+ assisted loss of the chloride ligand. 2,3 These attempts generally resulted in either no-reaction of the complexes on reasonable timescales or in decomposition of the complexes when the reactions were heated. Qualitative attempts to model these complexes with HyperChem ® supported significant charge on the metal center hindering loss of the chloride ligand. 2-4 In contrast however, we report here our successful attempts to remove the chloride ligand with Tl+ ion in complexes of the type trans- [ClRu(dppm) 2 (CCPh-4-Y)] where dppm = diphenylphosphinomethane and CCPh is a phenylacetylide derivative substituted in the 4-position with Y = H, NO 2 and OCH 3. Spectroscopic and Electrochemical Data Synthetic Scheme OHNH 2 Cl CH 3 H Br CHO NH 2 OHl CH 3 H Br CHO Reaction of trans-[ClRu(dppm) 2 CCPh] with Tl + followed via Cyclic Voltammetry Electron Withdrawing Effects of Acetylide Substituent Substituent IR UV-Vis E ½ V. -Y (KBr) v/cm-1 ( acetonitrile nm) V Ag-AgCl OCH 3 (C≡C) 2075 273 0.32 288 H (C≡C) 2072 309 0.41 268 NO 2 (C≡C) 2045 471 0.60 267 Dependence of Relative Rate Constant on E 1/2 www.rwu.edu