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Transannular Effects in Dicobalta−Superphane Complexes on the Mixed-Valence Class II/Class III Interface: Distinguishing between Spin and Charge Delocalization by Electrochemistry, Spectroscopy, and ab Initio Calculations

1999; American Chemical Society; Volume: 121; Issue: 40 Linguagem: Inglês

10.1021/ja9914792

1943-2984

M. E. Stoll, Sherri R. Lovelace, William E. Geiger, Holger Schimanke, Isabella Hyla‐Kryspin, Rolf Gleiter,

Metal-Catalyzed Oxygenation Mechanisms

The oxidative electron-transfer properties of several superphane complexes consisting of cyclopentadienylcobalt cyclobutadiene moieties linked by either three (compounds 1 and 4) or five (compounds 2 and 5) bridging methylene groups have been studied by experimental and theoretical methods. In both cases two separate one-electron oxidations are found. The mixed-valent monocations of the (−CH2−)5-bridged complexes are valence-trapped with very weak interactions between metal centers. The (−CH2−)3 complexes, however, have strong interactions between the two molecular halves. The intervalence transfer (IT) band of 1+ has characteristics of both class II (localized) and class III (delocalized) behavior, but the IR spectra of carboxy-labeled 4+ clearly establish trapped valence for the monocations of the propano-bridged systems. Photoelectron spectra and ab initio calculations at the UHF level show that, in the ground electronic state, 1+ has a half-filled orbital (i.e., electron spin) that is essentially localized in one Co dxy, orbital, but that the charges on the two metals are unequal owing to inductive electronic effects which give unequal electron flow from the ligands to the two metal centers. Calculations and IR (carbonyl) spectral shifts suggest about a 70:30 charge ratio between the two metal centers in 1+ and 4+, whereas both spin and charge localization is virtually complete in the pentano-bridged complexes 2+ and 5+. The intervalence transition in 1+ is proposed to proceed through a "hole"-transfer process mediated by a π-cyclobutadiene MO, ultimately involving a through-bond transannular mechanism.