An Experimental and Computational Investigation Rules Out Direct Nucleophilic Addition on the N2 Ligand in Manganese Dinitrogen Complex [Cp(CO)2Mn(N2)]

Author:

Le Dé Quentin1,Bouammali Amal1,Bijani Christian1,Vendier Laure1,del Rosal Iker2,Valyaev Dmitry A.1,Dinoi Chiara2,Simonneau Antoine1ORCID

Affiliation:

1. LCC-CNRS Université de Toulouse, CNRS, UPS 205 route de Narbonne, BP44099 31077 Toulouse cedex 4 France

2. LPCNO CNRS & INSA Université Paul Sabatier 135 Avenue de Rangueil 31077 Toulouse France

Abstract

AbstractWe have re‐examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] (1, Cp=η5‐cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li (3) that is stable only below −40 °C. Full characterization of 3 (including single crystal X‐ray diffraction) was performed. This complex decomposes quickly above −20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li (2). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so‐far unique behavior of the N2 ligand in 1. DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal‐coordinated N2 remains to be demonstrated.

Funder

H2020 European Research Council

Publisher

Wiley

Subject

General Chemistry,Catalysis

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