The preparation and properties of monometallic and bimetallic complexes of rhenium(I) tricarbonyl chloride coordinated to 4,4'-dimethyl-2,2'-bipyridine ((CH3)2bpy), 2,2'-bipyrimidine (bpm), 2,3-bis(2-pyridyl)pyrazine (bpp), and l,2-bis(4'-methyl-2,2'-bipyridyl-4-yl)ethane (Mebpy-Mebpy) are described. The CO stretching frequencies were in accord with facial geometry for the complexes. The NMR properties revealed that protons on the carbon atoms a to the coordinating nitrogen atoms of coordinated heterocycles were deshielded and shifted downfield. Electrochemically, one or two irreversible oxidations, a reversible reduction assignable to reduction of the heterocyclic ligand, and a second reduction (irreversible) at a potential more negative than that of the first were observed. The monometallic complexes displayed dir -* ir* transitions in the 360-380-nm region. The transition red-shifted to 454 nm for [(bpp)(Re(CO)3Cl)2] and to 480 nm for [(bpm)(Re(CO)3Cl)2] but remained at 366 nm for [(Mebpy-Mebpy)(Re(CO)3Cl)2], Emission was observed at room temperature for [((CH3)2bpy)Re(CO)3Cl], [(Mebpy-Mebpy)Re(CO)3Cl], [(bpp)Re(CO)3Cl], and [(Mebpy-Mebpy)(Re(CO)3Cl)2], Their emission maxima were located near 600 nm except for [(bpp)Re(CO)3Cl]. Its emission maximum was observed at 700 nm.84ER-13263 and the National Science Foundation under Grant CHE-8719709 for support. Supplementary Material Available: A listing of decoupling parameters, results, and conclusions for NMR experiments with [(Mebpy-Mebpy)-Re(CO)3Cl], [(bpp)Re(CO)3Cl], and [(bpp)(Re(CO)3Cl)2] (4 pages). Ordering information is given on any current masthead page.

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