Ligand Reactivity in Diarylamido/Bis(Phosphine) PNP Complexes of Mn(CO)3and Re(CO)3
Citations Over TimeTop 10% of 2009 papers
Abstract
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.
Related Papers
- → Terminal vs Bridging Hydrides of Diiron Dithiolates: Protonation of Fe2(dithiolate)(CO)2(PMe3)4(2012)128 cited
- → Protonation of homotroponeiron tricarbonyl and cyclooctatrienoneiron tricarbonyl complexes(1980)8 cited
- → 13C nuclear magnetic resonance study of the protonation of 2,2,4-trimethyl-1,5,9-triazacyclododecane(1988)6 cited
- → The effect of substitution on protonation sites: evidence for protonation at N(3) in N(7)-substituted adenine(1975)6 cited
- The Protonation Equili rium and Decomposition of Amino- and Hydroxyphosphonates, Phos phine Ox ides and Phosphonic Acid(2007)