Multifrequency Electron Paramagnetic Resonance Spectroscopy of Group Viib Carbonyl Radicals
Interest in organometallic 17e('-) free radical systems has increased dramatically due to their potential roles in catalytic processes. Multi-frequency electron paramagnetic resonance spectroscopy studies of (.)Mn(CO)(,3){P(n-Bu)(,3)}(,2), (.)Mn(CO)(,3){P(i-Bu)(,3)}(,2), (.)Mn(CO)(,3){P(i-Pr)(,3)}(,2') (.)Mn(CO)(,3){P(O-i-Pr)(,3)}(,2) and (.)Re(CO)(,3){P(cy)(,3)}(,2) (cy = cyclohexyl) were performed at conventional X-band ((DBLTURN) 9 GHz), S-band ((DBLTURN) 3 GHz) and L-band ((DBLTURN) 1 GHz) frequencies. Computer simulations of the X- and S-band frozen solution spectra as well as room temperature X-band solution spectra were obtained. Anisotropic g-shifts, metal hyperfine, and phosphorus super-hyperfine spin Hamiltonian parameters are reported and compared to values reported for (.)Mn(CO)(,5).
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University of Illinois at Urbana-Champaign