TY - DATA T1 - 2,2′-Pyridylpyrrolide Ligand Redistribution Following Reduction PY - 2013/05/06 AU - Keith Searles AU - Atanu K. Das AU - René W. Buell AU - Maren Pink AU - Chun-Hsing Chen AU - Kuntal Pal AU - David Gene Morgan AU - Daniel J. Mindiola AU - Kenneth G. Caulton UR - https://acs.figshare.com/articles/journal_contribution/2_2_Pyridylpyrrolide_Ligand_Redistribution_Following_Reduction/2418382 DO - 10.1021/ic400803e.s001 L4 - https://ndownloader.figshare.com/files/4060129 KW - quasireversible reductions KW - field ligand KW - ligand redistribution KW - Lewis acidity KW - CV evidence KW - Analogous ligand redistribution behavior KW - lattice toluene π cloud KW - CF 3 substituents KW - redox activity KW - Fe KW - CO KW - pyridylpyrrolide KW - KM KW - Cu KW - bulk metal KW - trimeric monovalent copper analogues N2 - The potential redox activity of the 2,2′-pyridylpyrrolide ligand carrying two CF3 substituents (L2) is investigated. Synthesis and characterization of d6 and d7 species M­(L2)2 for M = Fe and Co are described (both are nonplanar, but not tetrahedral), as are the Lewis acidity of each. In spite of CV evidence for quasireversible reductions to form M­(L2)2q– where q = 1 and 2, chemical reductants instead yield divalent metal complexes KM­(L2)3, which show attractive interactions of K+ to pyrrolide, to F, and to lattice toluene π cloud. The collected evidence on these products indicates that pyridylpyrrolide is a weak field ligand here, but CO can force spin pairing in Fe­(L2)2(CO)2. Evidence is presented that the overall reductive reaction yields 33 mol % of bulk metal, which is the fate of the reducing equivalents, and a mechanism for this ligand redistribution is proposed. Analogous ligand redistribution behavior is also seen for nickel and for trimeric monovalent copper analogues; reduction of Cu­(L2)2 simply forms Cu­(L2)2–. ER -