This award from the Inorganic, Bioinorganic and Organometallic Chemistry Program will support a study of the gas-phase chemistry of transition metal complexes for which the solution chemistry is already well-known. The study is expected to provide valuable information about the role of the solvent in solution-phase reactions of these substances. Gas-phase ion techniques, especially Fourier transform ion cyclotron resonance mass spectrometry, will be used to study the reactivity and thermodynamic properties of coordinatively saturated or near-saturated metal complexes which exist also as stable molecules or ions in the condensed phase. These experiments will both address fundamental questions regarding the intrinsic chemistry of such systems and provide insight into the effect of solvation on reactivity and thermochemistry. Classes of complexes to be investigated include: (1) early transition metal electrophilic cations of titanium, zirconium and hafnium, (2) organometallic and coordination complexes that have reversible one-electron changes, (3) electrophilic agostic complexes of cobalt(III) and rhodium(III), and (4) early transition element alkylidene and alkylidyne complexes. To provide improved thermodynamic data infrared multiphoton dissociation techniques will be entended to new wavelength ranges, and temperature control of ion cyclotron resonance spectrometry will be developed.
