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“Two‐Electron Reduction” of Phosphane‐substituted Tricobalt Clusters—Evidence for a 17‐Electron Intermediate in the Dissociative ETC Ligand Substitution
Author(s) -
Hinkelmann Klaus,
Mahlendorf Falko,
Heinze Jürgen,
Schacht HansThomas,
Field John S.,
Vahrenkamp Heinrich
Publication year - 1987
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198703521
Subject(s) - chemistry , ligand (biochemistry) , one electron reduction , reduction (mathematics) , substitution (logic) , cyclic voltammetry , electron , ion , photochemistry , crystallography , transformation (genetics) , electrochemistry , electrode , organic chemistry , physics , receptor , geometry , mathematics , quantum mechanics , computer science , programming language , biochemistry , gene
Reduction and ligand elimination result in reversible transformation of the μ 3 ‐alkylidyne complex 1 into the 17‐electron species 2 ⊙⊖ . This was confirmed by cyclic voltammetry and multisweep experiments with 1 as well as by trapping of the released phosphane ligand. The further reduction to 2 2⊖ is also reversible. The radical anion 2 ⊙⊖ , which is an essential 17‐electron intermediate for the ETC ligand exchange, is the first such species to be unequivocally detected.