| Autor: |
Ngo DX; Beckman Institute, and Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States., Del Ciello SA; Beckman Institute, and Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States., Barth AT; Beckman Institute, and Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States., Hadt RG; Beckman Institute, and Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States., Grubbs RH; Beckman Institute, and Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States., Gray HB; Beckman Institute, and Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States., McNicholas BJ; Beckman Institute, and Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 East California Boulevard, Mail Code 139-74, Pasadena, California 91125, United States. |
| Abstrakt: |
Complexes with the formula [M(diimine)(CN-BR 3 ) 4 ] 2- , where diimine = bipyridine (bpy), phenanthroline (phen), 3,5-trifluoromethylbipyridine (flpy), R = Ph, C 6 F 5 , and M = Fe II , Ru II , were synthesized and characterized by X-ray crystal structure analysis, UV-visible spectroscopy, IR spectroscopy, and voltammetry. Three highly soluble complexes, [Fe II (bpy)(CN-B(C 6 F 5 ) 3 ) 4 ] 2- , [Ru II (bpy)(CN-B(C 6 F 5 ) 3 ) 4 ] 2- , and [Ru II (flpy)(CN-B(C 6 F 5 ) 3 ) 4 ] 2- , exhibit electrochemically reversible redox reactions, with large potential differences between the bpy 0/- or flpy 0/- and M III/II couples of 3.27, 3.52, and 3.19 V, respectively. CASSCF+NEVPT2 calculations accurately reproduce the effects of borane coordination on the electronic structures and spectra of cyanometallates. |
