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Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Low-spin 1,1'-diphosphametallocenates of chromium and iron
Samuel M Greer1, Ökten Üngor2, Ross J Beattie3
1Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA. kiplinger@lanl.gov bstein@lanl.gov cgoodwin@lanl.gov and National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL 32310, USA and Department of Chemistry & Biochemistry, Florida State University, Tallahassee, FL 32306, USA.
Abstract:
We report two anionic diphosphametallocenates, [K(2.2.2-crypt)][M(PC4Me4)2] (M = Cr, 2-Cr; Fe, 2-Fe). Both are low-spin (S = ½) by EPR spectroscopy and SQUID magnetometry. This contrasts the high-spin (S = 3/2) ferrocenate, [K(2.2.2-crypt)][Fe(C5H2-1,2,4-tBu)2] (4-Fe). Quantum chemical calculations suggest this is due to significant differences in ligand field splitting of the d-orbitals which also explain structural features in the 2-M complexes.
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