title: Generating and stabilizing Co(I) in a nanocage environment.
abstract: A discrete nanocage of core-shell design, in which carboxylic acid groups were tethered to the core and silanol to the shell interior, was found to react with Co2(CO)8 to form and stabilize a Co(I)-CO species. The singular CO stretching band of this new Co species at 1958 cm(-1) and its magnetic susceptibility were consistent with Co(I) compounds. When exposed to O2, it transformed from an EPR inactive to an EPR active species indicative of oxidation of Co(I) to Co(II) with the formation of H2O2. It could be oxidized also by organoazide or water. Its residence in the nanocage interior was confirmed by size selectivity in the oxidation process and the fact that the entrapped Co species could not be accessed by an electrode.
authors.affiliation: Department of Chemical & Biological Engineering, ‡Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Jingmei
authors.initials: J
authors.lastname: Shen
authors.forename: Mayfair C
authors.initials: MC
authors.lastname: Kung
authors.forename: Zhongliang
authors.initials: Z
authors.lastname: Shen
authors.forename: Zhen
authors.initials: Z
authors.lastname: Wang
authors.forename: William A
authors.initials: WA
authors.lastname: Gunderson
authors.forename: Brian M
authors.initials: BM
authors.lastname: Hoffman
authors.forename: Harold H
authors.initials: HH
authors.lastname: Kung
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry*; D003035:Cobalt / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry; D012821:Silanes / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D012821:Silanes; C082343:silanol; D003035:Cobalt; D002248:Carbon Monoxide; D006861:Hydrogen Peroxide; D010100:Oxygen