Universität zu Köln

Jongbloed, Linda S., Vogt, Nicolas ORCID: 0000-0002-3437-4882, Sandleben, Aaron ORCID: 0000-0002-4141-7406, de Bruin, Bas ORCID: 0000-0002-3482-7669, Klein, Axel ORCID: 0000-0003-0093-9619 and van der Vlugt, Jarl Ivar (2018). Nickel-Alkyl Complexes with a Reactive PNC-Pincer Ligand. Eur. J. Inorg. Chem. (20-21). S. 2408 - 2419. WEINHEIM: WILEY-V C H VERLAG GMBH. ISSN 1099-0682

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Abstract

Based on previous work related to the design and application of rigid tridentate phosphine-pyridine-phenyl coordination offered by a PNC-pincer ligand upon cyclometalation to nickel, the synthesis, spectroscopic and solid state characterization and redox-reactivity of two Ni-II(PNC) complexes featuring either a methyl (2CH(3)) or CF3 co-ligand (2CF(3)) are described. One-electron oxidation is proposed to furnish C-C reductive elimination, as deduced from a combined chemical, electrochemical, spectroscopic and computational study. One-electron reduction results in a ligand-centered radical anion, as supported by electrochemistry, UV spectroelectrochemistry, EPR spectroscopy, and DFT calculations. This further attenuates the breadth of chemical reactivity offered by such PNC-pincer ligands.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Jongbloed, Linda S. UNSPECIFIED UNSPECIFIED UNSPECIFIED Vogt, Nicolas UNSPECIFIED orcid.org/0000-0002-3437-4882 UNSPECIFIED Sandleben, Aaron UNSPECIFIED orcid.org/0000-0002-4141-7406 UNSPECIFIED de Bruin, Bas UNSPECIFIED orcid.org/0000-0002-3482-7669 UNSPECIFIED Klein, Axel UNSPECIFIED orcid.org/0000-0003-0093-9619 UNSPECIFIED van der Vlugt, Jarl Ivar UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-182925
DOI:	10.1002/ejic.201800168
Journal or Publication Title:	Eur. J. Inorg. Chem.
Number:	20-21
Page Range:	S. 2408 - 2419
Date:	2018
Publisher:	WILEY-V C H VERLAG GMBH
Place of Publication:	WEINHEIM
ISSN:	1099-0682
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language DENSITY-FUNCTIONAL CALCULATIONS; ORDER REGULAR APPROXIMATION; HIGH-VALENT NICKEL; OXIDATIVE ADDITION; CORRELATION-ENERGY; BOND ACTIVATION; O-AMINOPHENOL; HARTREE-FOCK; BASIS-SETS; TRIFLUOROMETHYLATION Multiple languages Chemistry, Inorganic & Nuclear Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/18292