113597-92-5Relevant academic research and scientific papers
Reversible Binding of Dinitrogen and Dioxygen by a Ruthenium Picnic-Basket Porphyrin
Collman, James P.,Brauman, John I.,Fitzgerald, Jeffrey P.,Sparapany, John W.,Ibers, James A.
, p. 3486 - 3495 (2007/10/02)
We recently reported the synthesis and characterization of ruthenium picnic-basket porphyrin carbonyl complexes.These synthetic tetraarylporphyrins bear a rigid superstructure that defines a molecular cavity on one face of the porphyrin macrocycle.Photolysis of these carbonyl complexes in a coordinating solvent results in formation of bis-solvent complexes.The bis(pyridine) complex has been structurally characterized.General methods to control axial ligation in these ruthenium picnic-basket porphyrins are presented.A transient pentacoordinate ruthenium picnic-basket porphyrin, which reversibly binds both dinitrogen and dioxygen within the protected cavity has been prepared.The N2 and O2 complexes have been characterized by UV-visible, 1H NMR, and IR spectroscopies.The diamagnetic dioxygen complex shows ν(16O-16O) at 1103 cm-1 and thus is described as containing coordinated superoxide ion.A correlation between dioxygen binding and the Ru(III/II) potential was observed.
