pubs.acs.org/IC Published on Web 05/15/2009 r 2009 American Chemical Society 5234 Inorg. Chem. 2009, 48, 5234–5243 DOI: 10.1021/ic900223f Cobalt Complex as Building Blocks: Synthesis, Characterization, and Catalytic Applications of {Cd 2+ -Co 3+ -Cd 2+ } and {Hg 2+ -Co 3+ -Hg 2+ } Heterobimetallic Complexes Anurag Mishra, † Afsar Ali, † Shailesh Upreti, ‡ M. Stanley Whittingham, ‡ and Rajeev Gupta* ,† † Department of Chemistry, University of Delhi, Delhi - 110 007, India, and ‡ Department of Chemistry and Institute for Materials Research, State University of New York at Binghamton, Binghamton, New York 13902-6000 Received February 3, 2009 The present work demonstrates the utilization of the Co 3+ complex of pyridine-amide ligand as building blocks for the assembly of heterobimetallic complexes. These Co 3+ -centered building blocks orient the tethered pyridine groups to a preorganized cleft that successively coordinates to the Cd 2+ and Hg 2+ ions in the periphery. Both {Cd 2+ -Co 3+ -Cd 2+ } and {Hg 2+ -Co 3+ -Hg 2+ } heterobimetallic complexes have been thoroughly characterized, including crystal structures depicting interesting weak interactions in the solid state. The {Cd 2+ -Co 3+ -Cd 2+ } and {Hg 2+ -Co 3+ -Hg 2+ } heterobimetallic complexes have been further used for the catalytic cyanosilylation of imines and ring-opening reactions of oxiranes and thiiranes. The results suggest peripheral metal-selective catalytic reactions. Introduction Remarkable progress has been made in the area of mole- cular inorganic-organic hybrid compounds. These com- pounds hold promise as new materials with novel catalytic, magnetic, electronic, and optical properties. 1 Versatile syn- thetic approaches for the assembly of such structures from building blocks have been developed. 2 Considerable effort has been devoted to tune the building blocks as connectors and linkers in order to reach the stage of rational design with predictable architectures. 3 Most of the literature work is centered on developing the inorganic-organic hybrid com- pounds consisting of nondirectional ligands coordinated to the metal ions. There are very few reports on controlling the topology of the resultant metal-ligand structure. 4 Attempts to control the dimensionality and topology of these materials depend on the judicious selection of multidentate ligands with metal ions of appropriate coordination geometry. 5 Our approach is to design, synthesize, and utilize the coordination complexes as the building blocks for the con- struction of ordered structures. 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