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Cage Rearrangements in Dodecanuclear Co–Pt Dicarbido Clusters Promoted by Redox Reactions
Author(s) -
Femoni Cristina,
Iapalucci Maria Carmela,
Longoni Giuliano,
Zacchini Stefano,
Fedi Serena,
Fabrizi de Biani Fabrizia
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201101386
Subject(s) - chemistry , isostructural , redox , electrochemistry , metal , naphthalene , crystallography , stereochemistry , medicinal chemistry , inorganic chemistry , crystal structure , organic chemistry , electrode
The chemical reduction of [Co 8 Pt 4 C 2 (CO) 24 ] 2– ([ 1 ] 2– ) with Na/naphthalene results, after workup, in the isolation of either [Co 10 Pt 2 C 2 (CO) 22 ] 4– ([ 2 ] 4– ) or [Co 8 Pt 4 C 2 (CO) 20 ] 4– ([ 3 ] 4– ), depending on the experimental conditions. All these species undergo several chemical and/or electrochemical redox reactions, disclosing the existence of structurally related dodecanuclear clusters [ 1 ] n – ( n = 0–4), [ 2 ] n – ( n = 2–6) and [ 3 ] n – ( n = 1–7). In the attempt to isolate more reduced species,[ 1 ] n – , [ 2 ] n – and [ 3 ] n – undergo structural rearrangements resulting, among others, in the formation of the new species [Co 10– x Pt 2+ x C 2 (CO) 24 ] 2– ([ 4 ] 2– ) ( x = 0–2) structurally related to [ 1 ] 2– . These dodecanuclear M 12 C 2 dicarbido clusters are not isostructural and differ in the metal composition and/or the number of CO ligands. Nevertheless, they can be readily interconverted even if the interconversion reactions are not straightforward.