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Mechanistic Aspects of Redox‐Induced Assembly and Disassembly of S‐Bridged [2M‐2S] Structures
Author(s) -
Koch Felix,
Berkefeld Andreas,
Speiser Bernd,
Schubert Hartmut
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704599
Subject(s) - steric effects , redox , chemistry , metastability , ligand (biochemistry) , reactivity (psychology) , electron transfer , chemical stability , kinetic energy , chemical physics , computational chemistry , stereochemistry , photochemistry , organic chemistry , receptor , physics , medicine , biochemistry , alternative medicine , pathology , quantum mechanics
Sulfur‐bridged binuclear structures [2M‐2S] play a pivotal role in a variety of chemical processes such as bond breaking and formation and electron transfer. In general, structural persistence is deemed essential to the respective function but owing to the lack of a suitable molecular model system, the current understanding of the factors that control the thermodynamic and kinetic stability of [2M‐2S] cores clearly is limited. This work reports a series of binuclear complexes of nickel derived from a 1,4‐terphenyldithiophenol ligand platform that is ideally suited for mechanistic work to overcome this limitation. Redox‐induced assembly and disassembly of S‐bridged [2M‐2S] fragments have been investigated at the molecular level. As part of an extended square scheme, metastable binuclear structures that are significant mechanistically have been identified, characterized, and their reactivity studied quantitatively. Electronic properties that are inherent to [2M‐2S] structures and determine thermodynamic and kinetic stability are differentiated from steric effects imposed by co‐ligands.