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Dinuclear Copper( II ) Complexes of Two Homologous Pyrazine‐Based Bis(terdentate) Diamide Ligands
Author(s) -
Klingele née Hausmann Julia,
Moubaraki Boujemaa,
Murray Keith S.,
Boas John F.,
Brooker Sally
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.200400908
Subject(s) - chemistry , pyrazine , deprotonation , ligand (biochemistry) , electron paramagnetic resonance , crystallography , metal , stereochemistry , copper , medicinal chemistry , organic chemistry , ion , biochemistry , physics , receptor , nuclear magnetic resonance
The 1:1 reactions of the new bis(terdentate) diamide ligand N , N ' ‐bis(2‐pyridylmethyl)pyrazine‐2,5‐dicarboxamide(H 2 L 1 ) and its higher homologue N , N ' ‐bis[2‐(2‐pyridyl)ethyl]pyrazine‐2,5‐dicarboxamide (H 2 L 2 ) with Cu(BF 4 ) 2 · 4 H 2 O in the absence of added base have consistently afforded dicopper( II ) complexes of the doubly deprotonated ligands ( L 1 ) 2– and ( L 2 ) 2– . The complex [Cu II 2 ( L 2 )(H 2 O) 2 (MeCN) 2 ](BF 4 ) 2 ( 2a ) has been structurally characterised. Subsequently, reactions employing a correct stoichiometric 2:1 metal‐to‐ligand ratio in MeCN have afforded bulk samples of the dinuclear complexes. The compounds [Cu II 2 ( L 1 )(MeCN) 2 (H 2 O) 2 ](BF 4 ) 2 · H 2 O ( 1a· H 2 O) and [Cu II 2 ( L 2 )(H 2 O) 4 (BF 4 ) 2 ] · 2 H 2 O ( 2b· 2 H 2 O) have been structurally characterised. While complex 1a· H 2 O of the lower ligand homologue exhibits very weak antiferromagnetic spin coupling ( J = –0.24 cm –1 ), complex 2b of the higher ligand homologue exhibits very weak ferromagnetic spin coupling ( J = +0.67 cm –1 ). EPR studies have been carried out on polycrystalline powders and frozen DMF solutions of 1a· H 2 O and 2b· 2 H 2 O. The EPR spectra of the polycrystalline powders indicate the presence of dipolar broadening and weak intermolecular exchange, while those of the frozen DMF solutions are characteristic of dipolar‐coupled Cu II pairs within the dinuclear molecules, with no evidence of intra‐ or intermolecular exchange. The spectral simulations confirm that the binuclear structure and the Cu ··· Cu distances are retained in frozen solution. Dinuclear SiF 6 2– containing compounds, [Cu II 2 ( L 1 )(H 2 O) 4 ](SiF 6 ) ( 1b ) and {[Cu II 2 ( L 1 )(H 2 O) 2 (μ‐SiF 6 )] · 4 H 2 O} ∞ ( 1c· 4 H 2 O), were obtained serendipitously, in nearly quantitative yield, by the 2:1 reaction of Cu(BF 4 ) 2 · 4 H 2 O with H 2 L 1 in H 2 O. The unexpected SiF 6 2– anions were generated in the course of the reaction by partial hydrolysis of the BF 4 – anions employed, thus forming traces of HF which reacted with the glassware. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)