Ligand reactivity in diarylamido/bis(phosphine) PNP complexes of Mn(CO)3 and Re(CO)3.
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The syntheses of meridionally ligated tricarbonyl complexes (PNP)Mn(CO)(3) and (PNP)Re(CO)(3) are described (PNP = [2-P(CHMe(2))(2)-4-MeC(6)H(3)](2)N(-)). Cyclic voltammograms show reversible one-electron redox couples for both parent compounds (-0.34 V vs Cp(2)Fe(0/+) for (PNP)Mn(CO)(3), -0.25 V vs Cp(2)Fe(0/+) for (PNP)Re(CO)(3)), and chemical oxidation with AgOTf results in formation of the corresponding paramagnetic triflate salts [(PNP)Mn(CO)(3)]OTf and [(PNP)Re(CO)(3)]OTf. Electron paramagnetic resonance spectra and computational results indicate that this event is primarily ligand centered; allylation of the organic ligand moiety of [(PNP)Mn(CO)(3)]OTf with allyltributylstannane is consistent with this assignment. The oxidation (PNP)Mn(CO)(3) to [(PNP)Mn(CO)(3)]OTf results in a shift in average CO stretching frequency of 30 cm(-1); protonation of (PNP)Mn(CO)(3) with TfOH to form [(PNHP)Mn(CO)(3)]OTf results in a similar magnitude shift.
author list (cited authors)
Radosevich, A. T., Melnick, J. G., Stoian, S. A., Bacciu, D., Chen, C., Foxman, B. M., Ozerov, O. V., & Nocera, D. G.
complete list of authors
Radosevich, Alexander T||Melnick, Jonathan G||Stoian, Sebastian A||Bacciu, Deborha||Chen, Chun-Hsing||Foxman, Bruce M||Ozerov, Oleg V||Nocera, Daniel G