Low-spin 1, 1′-diphosphametallocenates of chromium and iron. Issue 5 (18th December 2020)

• Record Type: Journal Article
• Authors: Greer, Samuel M.; Üngor, Ökten; Beattie, Ross J.; Kiplinger, Jaqueline L.; Scott, Brian L.; Stein, Benjamin W.; Goodwin, Conrad A. P.
• Is Part Of: Chemical communications. Volume 57:Issue 5(2021)
• Page Start: 595
• Page End: 598
• Publication Date: 2020-12-18
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/d0cc06518h
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : We report two low-spin diphosphametallocenates [K(2.2.2-crypt)][M(PC4 Me4 )2 ] (M = Cr, Fe) and propose structural features that allow spin-control in 3d metallocenates. Abstract : We report two anionic diphosphametallocenates, [K(2.2.2-crypt)][M(PC4 Me4 )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 = ) ferrocenate, [K(2.2.2-crypt)][Fe(C5 H2 -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.