Synthesis, Structure, and Magnetic Studies of Manganese–Oxygen Clusters of Reduced Coordination Number, Featuring an Unchelated, 5-Coordinate Octanuclear Manganese Cluster with Water-Derived Oxo Ligands

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Department of Chemistry, Temple University, 1901 N. 13th Street, Philadelphia, Pennsylvania 19122, United States
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States
Cite this: Inorg. Chem. 2012, 51, 19, 10095–10104
Publication Date (Web):September 4, 2012
https://doi.org/10.1021/ic202448c
Copyright © 2012 American Chemical Society
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Abstract

The synthesis of reduced coordination (less than 6), unchelated manganese oxygen cluster systems is described. Addition of phenols to Mn(NR2)2 (R = SiMe3) results in protolytic amide ligand replacement, and represents the primary entry into the described chemistry. Addition of PhOH to Mn(NR2)2 results in the formation of the heteroleptic dimer Mn2(μ-OPh)2(NR2)2(THF)2 (1). Usage of the sterically larger 2,6-diphenylphenol (Ph2C6H3OH) as the ligand source results in the formation of a 3-coordinate heteroleptic dimer without THF coordination, Mn2(μ-OC6H3Ph2)2(NR2)2 (2). Attempts to generate 2 in the presence of THF or Et2O resulted in isolation of monomeric Mn(OC6H3Ph2)2L2 (3, L = THF, Et2O). Use of the sterically intermediate 2,4,6-trimethylphenol (MesOH) resulted in formation of the linear trinuclear cluster Mn3(μ-OMes)4(NR2)2(THF)2 (4). Reaction of Mn(NR2)2 with PhOH in the presence of water, or reaction of 1 with water, results in the formation of a 5-coordinate, unchelated Mn–O cluster, Mn85-O)2(μ-OPh)12(THF)6 (5). Preparation, structures, steric properties, and magnetic properties are presented. Notably, complex 5 exhibits a temperature-dependent phase transition between a 4-spin paramagnetic system at low temperature, and an 8-spin paramagnetic system at room temperature.

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Full crystallographic tables, crystallographic information files (CIF), NMR spectra, and EPR spectra of 5 in toluene. This material is available free of charge via the Internet at http://pubs.acs.org.

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