ic400803e_si_001.pdf (1.92 MB)
2,2′-Pyridylpyrrolide Ligand Redistribution Following Reduction
journal contributionposted on 2013-05-06, 00:00 authored by Keith Searles, Atanu K. Das, René W. Buell, Maren Pink, Chun-Hsing Chen, Kuntal Pal, David Gene Morgan, Daniel J. Mindiola, Kenneth G. Caulton
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–.