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Design, Preparation and Characterization of the Adducts of the Bis‐Amido Cobalticinium Complex [Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 N) 2 ][PF 6 ] with Fumaric and Maleic Acids
Author(s) -
Braga Dario,
Giaffreda Stefano L.,
Polito Marco,
Grepioni Fabrizia
Publication year - 2005
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.200500143
Subject(s) - chemistry , fumaric acid , dication , protonation , adduct , maleic acid , amide , supramolecular chemistry , cationic polymerization , medicinal chemistry , intramolecular force , dicarboxylic acid , stoichiometry , stereochemistry , crystallography , crystal structure , polymer chemistry , ion , organic chemistry , copolymer , polymer
The supramolecular hydrogen‐bonded adducts obtained by treating the cationic bis‐amido complex [Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 N) 2 ] + with fumaric and maleic acid are investigated and their modes of aggregation in the solid state are explored. It is shown that the bis‐amido organometallic complex can be mono‐ and di‐protonated in the reaction with the dicarboxylic acids, leading to the formation of complex, mixed‐anion supramolecular salts containing either the dication [Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 N)(η 5 ‐C 5 H 4 CONHC 5 H 4 NH)] 2+ , [ 1 H] 2+ , or the trication [Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 NH) 2 ] 3+ , [ 1 H 2 ] 3+ . The derivatives of the reaction with fumaric acid, namely, [Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 N)(η 5 ‐C 5 H 4 CONHC 5 H 4 NH)] 2+ · [PF 6 ] – · 1/2[fumarate] 2– , [ 1 H] 2+ · PF 6 – · 1/2[fumarate] 2– , and [Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 NH) 2 ] 3+ · [PF 6 ] – · [H(fumarate) 2 ] 3– · H 3 O + · H 2 O, [ 1 H 2 ] 3+ · [PF 6 ] – · [H(fumarate) 2 ] 3– · H 3 O + · H 2 O, contain either the dianion [fumarate] 2– or the hydrogen‐bridged supramolecular trianion [H(fumarate) 2 ] 3– , depending on the amide/acid stoichiometric ratio. In the case of maleic acid, on the other hand, the possibility of intramolecular hydrogen‐bond formation generates exclusively salts of the hydrogen maleate anions, namely, [Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 N)(η 5 ‐C 5 H 4 CONHC 5 H 4 NH)] 2+ · 5/2[PF 6 ] – · 3/2[Hmaleate] – , 2[ 1 H] 2+ · 5/2[PF 6 ] – · 3/2[Hmaleate] – , 2[Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 NH) 2 ] 3+ · 3[PF 6 ] – · 3[Hmaleate] – · 2H 2 O, 2[ 1 H 2 ] 3+ · 3[PF 6 ] – · 3[Hmaleate] – · 2H 2 O and [Co III (η 5 ‐C 5 H 4 CONHC 5 H 4 NH) 2 ] 3+ · 2[PF 6 ] – · [Hmaleate] – · H 2 O, [ 1 H 2 ] 3+ · 2[PF 6 ] – · [Hmaleate] – · H 2 O, in which the hydrogen maleate anions act as bridges between the protonated bis‐amido organometallic sandwiches. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)