Abstract
Metal-bipyridine complexes are a vehicle for developing approaches for studying the fluorescence of gas-phase ions; however, conclusions regarding fluorescence behavior depend on explicitly identifying the ionic species in the gas phase. [Ru(bpy)3]X 2 and [Os(bpy3)]X 2, (where bpy=2,2′-bipyridine and X=Cl or PF6), were studied using direct laser desorption (LD) and matrix-assisted laser desorption/ionization (MALDI) using Fourier transform mass spectrometry (FTMS). LD spectra of the PF6 salt of the Ru and Os complexes reveal counterion attachment, fluoride transfer, and significant losses of H for a number of peaks. LD of the chloride salt complexes produced loss of a single bpy ligand, chloride attachment, and losses of H. Spectra of [Ru(bpy3)]X 2 where X=BF −4 , CF3SO −3 , and SCN− were also collected using LD and compared with the spectra for Cl2 and PF6 salts. Regardless of counterion, loss of H is observed in LD spectra. MALDI spectra of the trisbipyridyl complexes using 2,5-dihydroxybenzoic acid (DHB) and sinapinic acid (SA) as the matrix were also obtained. The spectra using SA as matrix show intact molecular ion peaks with very little fragmentation and no counterion attachment. Unlike SA, the spectra obtained using DHB look similar to LD spectra with significant losses of H. Our results are consistent with a reaction scheme for hydrogen loss from a carbon that also involves breaking of the metal-nitrogen bond, rotation of a pyridine ring, and re-formation of an ortho-metallated complex by a metal-C bond. These results demonstrate the importance of ion generation method and the utilization of FTMS for correct characterization of metal poly(pyridyl) complexes.
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Kalyanasundaram, K. Polypyridyl Complexes of Ruthenium, Osmium, and Iron. Academic Press: London, 1992, pp 105–206.
Szulbinski, W. S.; Malato, S. Photocatalytic Wastewater Treatment Using the Zeolite-Y Entrapped Ruthenium Tris-2,2′-Bipyridine Complex. Polish J. Chem. 2001, 75, 1543–1551.
Sava, G.; Pacor, S.; Bregant, F.; Ceschia, V. Metal Complexes of Ruthenium—A Potential Class of Selective Anticancer Drugs. Anticancer Res 1991, 11, 1103–1107.
Milkevitch, M.; Shirley, B. W.; Brewer, K. J. Mixed-Metal Polymetallic Platinum Complexes Designed to Interact with DNA. Inorg. Chem. Acta 1997, 264, 249–256.
Scott, J. R.; Fairris, J. L.; McLean, M.; Wang, K. F.; Sligar, S. G.; Durham, B.; Millett, F. Intramolecular Electron-Transfer Reactions of Cytochrome B 5 Covalently Bonded to Ruthenium(II) Polypyridine Complexes: Reorganizational Energy and Pressure Effects. Inorg. Chim. Acta 1996, 243, 193–200.
Scott, J. R.; McLean, M.; Sligar, S. G.; Durham, B.; Millett, F. Effect of Binding Cytochrome C and Ionic-Strength on the Reorganizational Energy and Intramolecular Electron-Transfer in Cytochrome B 5 Labeled with Ruthenium(Ii) Polypyridine Complexes. J. Am. Chem. Soc. 1994, 116, 7356–7362.
Scott, J. R.; Willie, A.; McLean, M.; Stayton, P. S.; Sligar, S. G.; Durham, B.; Millett, F. Intramolecular Electron-Transfer in Cytochrome B 5 Labeled with Ruthenium(II) Polypyridine Complexes—Rate Measurements in the Marcus Inverted Region. J. Am. Chem. Soc. 1993, 115, 6820–6824.
Scott, J. R.; Tremblay, P. L.; Durham, B.; Ham, J. E. Design of a Fluorescence Lifetime Detection System for Ions Trapped in a Fourier Transform Mass Spectrometer. Proceeding of the 49th ASMS Conference; Chicago, IL, May, 2001, p A020612
Denti, G.; Serroni, S. Redox Processed of Ruthenium(II) Polypyridine Complexes Induced by Fast-Atom Bombardment Mass Spectrometry. J. Am. Soc. Mass Spectrom. 1993, 4, 306–311.
Miller, J. M.; Balasanmugam, K.; Nye, J.; Deacon, G. B.; Thomas, N. C. Observation of Doubly Charged Ions in Fast Atom Bombardment Mass Spectrometry: Ruthenium(Ii) Complexes in a Nitrobenzyl Alcohol Matrix. Inorg. Chem. 1987, 26, 560–562.
Bojesen, G. Fast Atom Bombardment Mass Spectrometry of Coordination Compounds. Org. Mass Spectrom. 1985, 20, 413–415.
Cerny, R. L.; Sullivan, B. P.; Bursey, M. M.; Meyer, T. J. Fast Atom Bombardment and Field Desorption Mass Spectrometry of Organometallic Derivatives of Ruthenium(II) and Osmium(II). Inorg. Chem. 1985, 24, 397–401.
Liang, X.; Suwanrumpha, S.; Freas, R. B. Fast Atom Bombardment Tandem Mass Spectrometry of (Polypyridyl)Ruthenium(II) Complexes. Inorg. Chem. 1991, 30, 652–658.
Balasanmugam, K.; Day, R. J.; Hercules, D. M. Characterization of O-Phenanthroline and 2,2′-Bipyridine Complexes by Laser Mass Spectrometry. Inorg. Chem. 1985, 23, 4477–4483.
Beavis, R.; Lindner, J.; Grotenmeyer, J.; Atkinson, I. M.; Keene, F. R.; Knight, A. E. W. Co2-Laser Desorption and Multiphoton Ionization of Tris(2,2′-Bipyridyl)Ruthenium. J. Am. Chem. Soc. 1988, 110, 7534–7535.
Hunsucker, S. W.; Watson, R. C.; Tissue, B. M. Characterization of Inorganic Coordination Complexes by Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry. Rapid Commun. Mass Spectrom. 2001, 15, 1334–1340.
Durham, B.; Walsh, J. L.; Carter, C. L.; Meyer, T. J. Synthetic Applications of Photosubstitution Reactions of Poly(Pyridyl) Complexes of Ruthenium(II). Inorg. Chem. 1980, 19, 860–865.
Constable, E. C.; Raithby, P. R.; Smit, D. N. The X-Ray Crystal Structure of Tris(2,2′-Bipyridine)Osmium(II) Hexafluorophosphate. Polyhedron 1989, 8, 367–369.
Shepherd, D. G. Elements of Fluid Mechanics. Harcourt, Brace, and World Inc.: New York, 1965, pp 159–163.
Yao, J.; Dey, M.; Pastor, S. J.; Wilkins, C. L. Analysis of High-Mass Biomolecules Using Electrostatic Fields and Matrix-Assisted Laser Desorption/Ionization in a Fourier Transform Mass Spectrometer. Anal. Chem. 1995, 67, 3638–3642.
Scott, J. R.; Tremblay, P. L. Highly Reproducible Laser Beam Scanning Device for an Internal Source Laser Desorption Microprobe Fourier Transform Mass Spectrometer. Rev. Sci. Instrum. 2002, 73, 1108–1116.
McJunkin, T. R.; Tremblay, P. L.; Scott, J. R. Automation and Control of an Imaging Internal Laser Desorption Fourier Transform Mass Spectrometer. JALA 2002, 7, 76–83.
Karas, M.; Gluckmann, M.; Schafer, J. Ionization in Matrix-Assisted Laser Desorption/Ionization: Singly Charged Molecular Ions are the Lucky Survivors. J. Mass Spectrom 2000, 35, 1–12.
Sprouse, S.; King, K. A.; Spellane, P. J.; Watts, R. J. Photophysical Effects Fo Metal-Carbon O Bonds in Ortho-Metalated Complexes of Ir(III) and Rh(III). J. Am. Chem. Soc. 1984, 106, 6647–6653.
Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry: Principles of Structure and Reactivity. Harper Collins College Publishers: New York, 1993, pp 590–591.
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Published online March 18, 2003
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Ham, J.E., Durham, B. & Scott, J.R. Comparison of laser desorption and matrix-assisted laser desorption/ionization for ruthenium and osmium trisbipyridine complexes using Fourier transform mass spectrometry. J Am Soc Mass Spectrom 14, 393–400 (2003). https://doi.org/10.1016/S1044-0305(03)00069-2
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DOI: https://doi.org/10.1016/S1044-0305(03)00069-2