A rare low-spin Co\(^{IV}\)Bis(\(\beta\)-silyldiamide) with high thermal stability

Attempted preparation of a chelated Co\(^{IV}\) \(\beta\)-silylamide resulted in the unprecedented disproportionation to Co\(^{0}\) and a spirocyclic cobalt(IV) bis(\(\beta\)-silyldiamide): [Co[(N\(^{t}\)Bu)\(_2\)SiMe\(_2\)]\(_2\)] (1). Compound 1 exhibited 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 for tetrahedral Co\(^{IV}\). Ab initio semicanonical coupled-cluster calculations (DLPNO-CCSD(T)) revealed the doublet state was clearly preferred (−27 kcal mol\(^{−1}\)) over higher spin configurations only for the bulky tert-butyl-substituted analogue. Unlike other Co\(^{IV}\) complexes, 1 had remarkable thermal stability, and was demonstrated to form a stable self-limiting monolayer in preliminary atomic layer deposition (ALD) surface saturation experiments. The ease of synthesis and high stability make 1 an attractive starting point to investigate otherwise inaccessible Co\(^{IV}\) intermediates and for synthesizing new materials.

Metadaten
Author:	David Zanders ORCiD GND, Goran Bačić ORCiD GND, Dominique Leckie ORCiD GND, Oluwadamilola Odegbesan ORCiD GND, Jeremy Rawson ORCiD GND, Jason D. Masuda ORCiD GND, Anjana Devi ORCiD GND, Seán Thomas Barry ORCiD GND
URN:	urn:nbn:de:hbz:294-98628
DOI:	https://doi.org/10.1002/anie.202001518
Parent Title (English):	Angewandte Chemie International Edition
Subtitle (English):	steric enforcement of a doublet configuration
Publisher:	Wiley-VCH
Place of publication:	Hoboken, New Jersey
Document Type:	Article
Language:	English
Date of Publication (online):	2023/05/05
Date of first Publication:	2020/05/05
Publishing Institution:	Ruhr-Universität Bochum, Universitätsbibliothek
Tag:	EPR spectroscopy; atomic layer deposition; cobalt; coupled-cluster calculations; density functional calculations
Volume:	59
Issue:	33
First Page:	14138
Last Page:	14142
Note:	Dieser Beitrag ist auf Grund des DEAL-Wiley-Vertrages frei zugänglich.
Institutes/Facilities:	Lehrstuhl für Anorganische Chemie II, Inorganic Materials Chemistry
Dewey Decimal Classification:	Naturwissenschaften und Mathematik / Chemie, Kristallographie, Mineralogie
open_access (DINI-Set):	open_access
faculties:	Fakultät für Chemie und Biochemie
Licence (English):	Creative Commons - CC BY 4.0 - Attribution 4.0 International

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