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Isovalent Ag III /Ag III , Ag II /Ag II , Mixed‐Valent Ag II /Ag III , and Corrolato‐Based Mixed‐Valency in β,β′‐Linked [Bis{corrolato‐silver}] n Complexes
Author(s) -
Patra Bratati,
Sobottka Sebastian,
Sinha Woormileela,
Sarkar Biprajit,
Kar Sanjib
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.201703512
Subject(s) - valency , chemistry , redox , crystallography , metal , electrochemistry , copper , inorganic chemistry , stereochemistry , organic chemistry , linguistics , philosophy , electrode
Mixed‐valent compounds are fascinating entities that are useful as models for investigating electron‐transfer reactions, and find use in a host of biologically relevant redox processes. Though the bio‐relevant metal copper is well established in mixed‐valent chemistry, the Ag II /Ag III mixed‐valent combination of its higher congener in a molecular complex has rarely been reported before. This work reports the synthesis of a new β,β′‐linked bis{corrolato‐silver(III)} complex and its characterization in five different redox states. A combination of electrochemistry, spectroelectrochemistry, and DFT calculations point to the existence of a mixed‐valent Ag II /Ag III and an isovalent Ag II /Ag II form. Additionally, characterization of the Ag III /Ag III form and ligand‐based corrolato‐centered mixed‐valency is presented as well. These results thus open new avenues for bis‐corrolato ligands and for mixed‐valency in disilver compounds.