Synthesis, structure, and thermal behavior of discrete Co(II), Ag(I), and Pd(II) complexes with 2,3-bis(2-pyridyl)quinoxaline. Insight into coordination modes

The reactions of 2,3-bis(2-pyridyl)quinoxaline (bpq) with CoCl2. 6H(2)O, Ag(CH3CN)(4)BF4, and PdCl2(C6H5CN)(2) produce [CoCl2(bpq)](2). 2CHCl(3), [Ag(bpq)CH3CN](2)(BF4)(2). 2CH(3)CN, and [PdCl2(bpq)], respectively. All the products are discrete 1:1 (metal:bpq) adducts, where the chelation mode of the bpq is dependent upon the metal atoms. The structure of [CoCl2(bpq)](2). 2CHCl(3) is a centrosymmetric Cl-bridged four-membered dimer, [Co2Cl2], in which the bpq is bonded to the cobalt(IT) atom in an anisobidentate mode with the nitrogen donors of pyridine and pyrazine rings. For [Ag(bpq)CH3CN](2)(BF4)(2). 2CH(3)CN, each bpq ligand connects two tetrahedral silver(I) ions in a tridentate mode, resulting in a cationic cyclic dimer. The structure of [PdCl2(bpq)] approximates to a molecular rocking chair with an isobidentate bpq through the nitrogen donors of 2-pyridyl rings. The compounds exhibit significant and characteristic relationships between the structures and their thermal properties. For [CoCl2(bpq)](2). 2CHCl(3), the solvate chloroform molecules are safely contained up to 144 degreesC, but drastically evaporate above this temperature. The striking feature of [Ag(bpq)CH3CN](2)(BF4)(2). 2CH(3)CN is that the skeletal cyclic dimer is basically retained after dissociation of the coordinated acetonitriles in the solid state. (C) 2001 Elsevier Science B.V. All rights reserved.