title: Photochemical activation of an azido manganese-monosubstituted keggin polyoxometalate: on the road to a Mn(V)-nitrido derivative.
abstract: The manganese(V)-nitrido polyoxometalate derivative [PW(11)O(39){Mn(V)N}](5-) has been synthesized by photochemical activation of the parent manganese(III)-azido derivative [PW(11)O(39)Mn(III)N(3)](5-). It was characterized by mass spectrometry, (31)P NMR, UV-vis, and IR spectroscopies. An electrochemistry study indicated that only the Mn(V) state was stable. The photoactivation of the manganese(III)-azido derivative proceeds through two competitive routes, yielding to the targeted product of photooxidation {Mn(V)N} or the undesirable product of photoreduction {Mn(II)L} (L = H(2)O, N(3)), depending on the photolysis conditions. A simplified photolysis mechanism involving two different excited states was proposed to account for the temperature and wavelength dependence.
authors.affiliation: Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, Equipe Polyoxométallates Case courier 42, UPMC Univ Paris 06, 4 place Jussieu, 75252 Paris cedex 05, France.
authors.forename: G
authors.initials: G
authors.lastname: Izzet
authors.forename: E
authors.initials: E
authors.lastname: Ishow
authors.forename: J
authors.initials: J
authors.lastname: Delaire
authors.forename: C
authors.initials: C
authors.lastname: Afonso
authors.forename: J-C
authors.initials: JC
authors.lastname: Tabet
authors.forename: A
authors.initials: A
authors.lastname: Proust
mesh_terms: D001386:Azides / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010777:Photochemistry; D017973:Tungsten Compounds / Q000737:chemistry*; D000099294:Polyoxometalates
chemical_list: D001386:Azides; D008345:Manganese; D009942:Organometallic Compounds; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates