High-Field Solid-State 99Ru NMR Spectroscopy in Inorganic and Organometallic Ruthenium Compounds
EMSL Project ID
3363
Abstract
Ruthenium and its compounds play an important role in many areas of chemistry. They are used extensively as catalysts as well as in energy transfer reactions. Despite ruthenium?s importance, NMR spectroscopic data is extremely limited. Ruthenium-99 is the most promising NMR active isotope of Ru; however, fewer than 25 99Ru NMR papers have been published in total. The solid-state NMR work has been limited to magnetic and superconducting ruthenium compounds. The lack of Ru NMR data for diamagnetic compounds is a result of the unfavorable magnetic properties of the NMR active ruthenium nuclei, 99Ru and 101Ru; both of which are quadrupolar nuclei, with spin 5/2, with quite different quadrupole moments: 0.079 barn and 0.457 barn respectively. The two isotopes are only present in moderate natural abundance and both are significantly low- nuclei. Through the use of high magnetic fields and new experimental techniques these obstacles can be overcome and a great deal of information can be extracted from the solid-state NMR spectra. We will perform 99Ru NMR spectroscopy experiments on solid diamagnetic ruthenium compounds, examining a number of octahedral, organometallic compounds and characterize the Ru chemical shift and electric field gradient tensors. These results will be compared with high-level density functional theory (DFT) calculations that include relativistic effects for the ruthenium nucleus. The use of the highest applied magnetic field possible is desired in order to obtain maximum sensitivity, to reduce second-order quadrupolar broadening, and to facilitate measurement of the chemical shift tensors.
Project Details
Project type
Capability Research
Start Date
2003-04-12
End Date
2004-04-26
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Ooms KJ, and RE Wasylishen. 2004. "Solid-State Ru-99 NMR Spectroscopy: A Useful Tool for Characterizing Prototypal Diamagnetic Ruthenium Compounds
." Journal of the American Chemical Society 126(35):10972-10980.