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Issue 14, 2020
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Completing the triad: synthesis and full characterization of homoleptic and heteroleptic carbonyl and nitrosyl complexes of the group VI metals

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Abstract

Oxidation of M(CO)6 (M = Cr, Mo, W) with the synergistic oxidative system Ag[WCA]/0.5 I2 yields the fully characterized metalloradical salts [M(CO)6]+˙[WCA] (weakly coordinating anion WCA = [F-{Al(ORF)3}2], RF = C(CF3)3). The new metalloradical cations with M = Mo and W showcase a similar structural fluxionality as the previously reported [Cr(CO)6]+˙. Their reactivity increases from M = Cr < Mo < W and their syntheses allow for in-depth insights into the properties of the group 6 carbonyl triad. Furthermore, the reaction of NO+[WCA] with neutral carbonyl complexes M(CO)6 gives access to the heteroleptic carbonyl/nitrosyl cations [M(CO)5(NO)]+ as salts of the WCA [Al(ORF)4], the first complete transition metal triad of their kind.

Graphical abstract: Completing the triad: synthesis and full characterization of homoleptic and heteroleptic carbonyl and nitrosyl complexes of the group VI metals

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Article information


Submitted
19 Dec 2019
Accepted
01 Mar 2020
First published
06 Mar 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 3592-3603
Article type
Edge Article

Completing the triad: synthesis and full characterization of homoleptic and heteroleptic carbonyl and nitrosyl complexes of the group VI metals

J. Bohnenberger, M. Schmitt, W. Feuerstein, I. Krummenacher, B. Butschke, J. Czajka, P. J. Malinowski, F. Breher and I. Krossing, Chem. Sci., 2020, 11, 3592
DOI: 10.1039/C9SC06445A

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