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A Rare Low Spin Co(IV) Bis-Silyldiamide with High Thermal Stability: Exploring the Origin of an Unusual S = 1/2 Configuration

preprint
revised on 25.01.2020 and posted on 27.01.2020 by David Zanders, Goran Bačić, Dominique Leckie, Oluwadamilola Odegbesan, Jeremy M. Rawson, Jason Masuda, Anjana Devi, Sean Barry
Attempted preparation of a chelated Co(II) β-silylamide re-sulted in the unprecedented disproportionation to Co(0) and a spirocyclic cobalt(IV) bis(β-silyldiamide): [Co[(NtBu)2SiMe2]2] (1). Compound 1 exhibits a room temperature magnetic moment of 1.8 B.M and a solid state axial EPR spectrum diagnostic of a rare S = 1/2 configuration. Semicanonical coupled-cluster calculations (DLPNO-CCSD(T)) revealed the doublet state was clearly preferred (–27 kcal/mol) over higher spin configurations for which density functional theory (DFT) showed no energetic preference. Unlike other Co(IV) complexes, 1 had remarkable thermal stability, and was demonstrated to form a stable self-limiting monolayer in initial atomic layer deposition (ALD) surface saturation tests. The ease of synthesis and high-stability make 1 an attractive starting point to begin investigating otherwise inaccessible Co(IV) intermediates and synthesizing new materials.

Funding

SFB-TR87

NSERC, RGPIN-2019-06213

QEII-OGSST

DAAD-1-year fellow program

Kekulé fellowship program

History

Email Address of Submitting Author

david.zanders@rub.de

Institution

Ruhr University Bochum / Carleton University

Country

Germany / Canada

ORCID For Submitting Author

0000-0001-5516-7738

Declaration of Conflict of Interest

no conflict of interest

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