Low-spin 1,1′-diphosphametallocenates of chromium and iron

We report two anionic diphosphametallocenates, [K(2.2.2-crypt)][M(PC 4 Me 4 ) 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 = &z.frac32;) ferrocenate, [K(2.2.2-crypt)][Fe(C 5 H 2 -1,2,4- t Bu) 2 ] ( 4-Fe )....

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2021-01, Vol.57 (5), p.595-598
Main Authors: Greer, Samuel M, Üngor, Ökten, Beattie, Ross J, Kiplinger, Jaqueline L, Scott, Brian L, Stein, Benjamin W, Goodwin, Conrad A. P
Format: Article
Language:English
Subjects:
Chromium
Crystallography
Iron
Magnetic measurement
Quantum chemistry
Superconducting quantum interference devices
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Summary:We report two anionic diphosphametallocenates, [K(2.2.2-crypt)][M(PC 4 Me 4 ) 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 = &z.frac32;) ferrocenate, [K(2.2.2-crypt)][Fe(C 5 H 2 -1,2,4- t Bu) 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. We report two low-spin diphosphametallocenates [K(2.2.2-crypt)][M(PC 4 Me 4 ) 2 ] (M = Cr, Fe) and propose structural features that allow spin-control in 3d metallocenates.
ISSN:1359-7345
1364-548X
DOI:10.1039/d0cc06518h