Self-Assembled Transition-Metal Macrocycles and Two-Dimensional Coordination Polymers Derived from Flexible C2co2 Cluster-Bridged Bipyridine Ligands [(4-C5h4nco2ch2)(2)c2co2(co)(6)] and [(3-C5h4nco2ch2)(2)c2co2(co)(6)]

Reactions of the tetrahedral C2Co2 cluster-bridged bipyridine ligand [(4-C5H4NCO2CH2)(2)C2Co2(CO)(6)] (L-a) with [{M(dppb)-(H2O)(2)}(OTf)(2)] (M = Pd, Pt; dppb = 1,4-bis(diphenylphosphanyl)butane; OTf = SO3CF3) and AgX (X = NO3, SbF6) gave cationic metallamacrocycles [(M(dppb)L-a)(2)(OTf)(4)] (1, M = Pd; 2, M = Pt) and [(AgLa)(2)X-2] (3, X = NO3; 4, X = SbF6), Furthermore, the isomeric C2Co2 cluster-bridged bipyridine ligand [(3-C5H4NCO2CH2)(2)C2Co2(CO)(6)] (L-b) reacted with ZnCl2 and AgX (X = PF6, ClO4) to afford cationic macrocycle [((ZnLCl2)-Cl-b)(2)] (5) and coordination polymers [((AgLX)-X-b)(n)] (6, X = PF6; 7, X = ClO4), respectively. Whereas flexible ligand L-a is known, L-b is new and could be prepared by reaction of but-2-yne-1,4-diyl dipyridine-3-carboxylate with [Co-2(CO)(8)]. New self-assembled products 1-7 and ligand L-b were characterized by elemental analysis and spectroscopy, and 1, 3-7, and L-b were additionally characterized by X-ray crystallography. In addition, the electrochemistry of L-b and 5 Were studied by cyclic voltammetry. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)