title: Ligand reactivity in diarylamido/bis(phosphine) PNP complexes of Mn(CO)3 and Re(CO)3.
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.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Alexander T
authors.initials: AT
authors.lastname: Radosevich
authors.forename: Jonathan G
authors.initials: JG
authors.lastname: Melnick
authors.forename: Sebastian A
authors.initials: SA
authors.lastname: Stoian
authors.forename: Deborha
authors.initials: D
authors.lastname: Bacciu
authors.forename: Chun-Hsing
authors.initials: CH
authors.lastname: Chen
authors.forename: Bruce M
authors.initials: BM
authors.lastname: Foxman
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Ozerov
authors.forename: Daniel G
authors.initials: DG
authors.lastname: Nocera
mesh_terms: D002384:Catalysis; D004563:Electrochemistry; D008024:Ligands; D008345:Manganese / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D010777:Photochemistry / Q000379:methods*; D012211:Rhenium / Q000737:chemistry*
chemical_list: D008024:Ligands; D010720:Phosphines; D008345:Manganese; D012211:Rhenium; C044646:phosphine; D010100:Oxygen