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• W2079591811 abstract "The organonitrile or carbonyl complexes cis -[ReCl(RCN)(dppe) 2 ] ( 1 ) (R = 4-Et 2 NC 6 H 4 ( 1a ), 4-MeOC 6 H 4 ( 1b ), 4-MeC 6 H 4 ( 1c ), C 6 H 5 ( 1d ), 4-FC 6 H 4 ( 1e ), 4-ClC 6 H 4 ( 1f ), 4-O 2 NC 6 H 4 ( 1g ), 4-ClC 6 H 4 CH 2 ( 1h ), t -Bu ( 1i ); dppe = Ph 2 PCH 2 CH 2 PPh 2 ), or cis -[ReCl(CO)(dppe) 2 ] ( 2 ), as well as trans -[FeBr(RCN)(depe) 2 ]BF 4 ( 3 ) (R = 4-MeOC 6 H 4 ( 3a ), 4-MeC 6 H 4 ( 3b ), C 6 H 5 ( 3c ), 4-FC 6 H 4 ( 3d ), 4-O 2 NC 6 H 4 ( 3e ), Me ( 3f ), Et ( 3g ), 4-MeOC 6 H 4 CH 2 ( 3h ); depe = Et 2 PCH 2 CH 2 PEt 2 ), novel trans -[FeBr(CO)(depe) 2 ]BF 4 ( 4 ) and trans -[FeBr 2 (depe) 2 ] ( 5 ) undergo, as revealed by cyclic voltammetry at a Pt-electrode and in aprotic non-aqueous medium, two consecutive reversible or partly reversible one-electron oxidations assigned as Re I → Re II → Re III or Fe II → Fe III → Fe IV . The corresponding values of the oxidation potentials I E 1/2 ox and II E 1/2 ox (waves I and II, respectively) correlate with the Pickett's and Lever's electrochemical ligand and metal site parameters. This allows to estimate these parameters for the various nitrile ligands, depe and binding sites (for the first time for a Fe III/IV couple). The electrochemical ligand parameter show dependence on the electron-richness of the metal centre. The values of I E 1/2 ox for the Re I complexes provide some supporting for a curved overall relationship with the sum of Lever's electrochemical ligand parameter. The Pickett parametrization for closed-shell complexes is extended now also to 17-electron complexes, i.e. with the 15-electron Re II and Fe III centres in cis -{[ReCl(dppe) 2 ]} + and trans -{FeBr(depe) 2 } 2+ , respectively." @default.
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• W2079591811 date "2001-01-01" @default.
• W2079591811 modified "2023-10-03" @default.
• W2079591811 title "Redox Potential - (Electronic) Structure Relationships in 18- and 17-Electron Mononitrile (or Monocarbonyl) Diphosphine Complexes of Re and Fe" @default.
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• W2079591811 doi "https://doi.org/10.1135/cccc20010139" @default.
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