Cationic ligands for Ag(I): Organometallic polymers versus unimolecular complexes |
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Authors: | Darren D.J.W. Mercer |
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Affiliation: | Department of Chemistry, Saint Mary’s University, Halifax, Nova Scotia, Canada B3K 3Z2 |
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Abstract: | We have prepared and characterized two cationic ligands and their Ag(I) coordination compounds. For the bidentate ligand 2, 2,2-bis-pyridin-2-ylmethyl-2,3-dihydro-1H-isoindolium bromide, we obtained the organometallic polymer [AgL]x[CF3SO3]2x (4), and the unimolecular complex [AgL2][PF6]3 (5). Compound 4 exists as an organometallic linear polymer with triflate anions either bonded to Ag(I) or non-bonded and sandwiched between the polymer chains. Complex 5 is the only unimolecular example in this series due to the non-interaction of anions with Ag(I) or with the cationic portion of the ligand. In the case of the tridentate cationic ligand 3-(3-pyridin-2-yl-2-pyridin-2-ylmethy-propyl)-benzyl-triethylammonium bromide (3), two dimeric Ag(I) complexes are formed, [Ag2L2][CF3SO3]4 (6), and [Ag2(CH3CN2)2L2][PF6]4 (7). Both of these dimers have essentially similar structures, with a closed-shell Ag(I)?Ag(I) interaction of approximately 3.00 Å in both cases; the pyridyl moieties of the ligands are forced into an electronically unfavourable face-to-face arrangement. The coordination spheres of the Ag(I) cations are completed by in the case of 6, and by CH3CN solvent in the case of 7. In the extended packing diagrams, the arrangements of 6 and 7 are driven by intermolecular π-stacking and cation-anion interactions. |
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Keywords: | Cationic ligands Silver(I) Coordination complexes Nitrogen ligands Organometallic polymers |
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