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Construction of Bimetallic and Trimetallic Aggregates with a [Y(COT)2]- Building Block: Solid-State Structures and
Zheng Zhou1,2, Aaron J Babson1, Zheng Wei1
1Department of Chemistry, University at Albany, State University of New York, Albany, New York 12222, United States.
None:
Several new bimetallic and trimetallic complexes containing the [Y-(COT)2]- unit in different coordination environments are synthesized and fully characterized using X-ray crystallography and NMR spectroscopy. These complexes include [K([2.2.2]-cryptand)]-[Y-(COT)2] (1), [K-(18-crown-6)-(THF)]-[Y-(COT)2] (2), [Y2K2(COT)4(THF)4] (3), and [YKCa-(COT)3(THF)3] (4). In the presence of secondary ligands, bimetallic ionic pairs that comprise a [Y-(COT)2]- sandwich and a solvent-wrapped K+ ion are formed in 1 and 2. In contrast, 3 represents a bimetallic tetradecker oligomer with two [Y-(COT)2]- units bridged by a K+ ion and a terminal [K-(THF)4]+ moiety. Complex 4 is a heterotrimetallic triple-decker with an axial arrangement of three metal centers to form [Y-(COT)2K-(COT)-Ca-(THF)3]. Structural analysis shows the Y-COTcentroid distances in the [Y-(COT)2]- sandwich are equidistant (1.884(6) Å) in 1 but become asymmetric in 2-4 (1.857(3)-1.952(3) Å), reflecting additional external coordination. The two COT rings are parallel in 1 and become increasingly tilted from 0.8 to 27.5° in 2-4, respectively. Multinuclear NMR spectroscopy measurements reveal the solution behavior of the sandwich and heterometallic multidecker COT-based products. The observed NMR spectroscopic trends corroborate with weak interactions between the [Y-(COT)2]- unit and cationic moieties persisting in solutions of 2-4.
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