Pseudohalide complexation by manganese 12-metallacrowns-4 complexes》.pdf

/locate/ica Inorganica Chimica Acta 331 (2002) 73–80 Pseudohalide complexation by manganese 12-metallacrowns-4 complexes Dimitris P. Kessissoglou a,*, Jeffrey J. Bodwin b, Jeff Kampf b, Catherine Dendrinou-Samara a, Vincent L. Pecoraro b, * a Department of Chemistry, Aristotle Uniersity of Thessaloniki, Thessaloniki 54006, Greece b Department of Chemistry, Uniersity of Michigan, Ann Arbor, MI 48109 -1055, USA Received 27 June 2001; accepted 19 September 2001 Dedicated to Professor A.G. Sykes Abstract The reaction of manganese chloride, sodium or potassium thiocyanate and salicylhydroxamic acid in dimethylformamide– methanol solution leads to the formation of the 12-membered metallacrowns [Na(dmf) ] (SCN) {[12-MC -4](dmf) } (1) 2 2 2 Mn(III)N(shi) 4 and [K(dmf) ] (SCN) {[12-MC -4](dmf) } (2). The crystal structure analyses of 1 and 2 show that pseudohalide ligands 2 2 2 Mn(III)N(shi) 4 are bound to the ring manganese ions through the N atoms, while the alkaline ions, Na + or K+, are accommodated at the cavity of the metallacrown ring. The alkali cations are bound to four oxygen atoms of the metallacrown ring and a single axial dmf. The binding of the pseudohalides (SCN − − −