TY - JOUR

T1 - NHCs as Neutral Donors towards Polyphosphorus Complexes

AU - Riedlberger, Felix

AU - Todisco, Stefano

AU - Mastrorilli, Piero

AU - Timoshkin, Alexey Y.

AU - Seidl, Michael

AU - Scheer, Manfred

N1 - Funding Information: This work was supported by the Deutsche Forschungsgemeinschaft (DFG) within the project Sche 384/38‐1. Open access funding enabled and organized by Projekt DEAL. Publisher Copyright: © 2020 The Authors. Published by Wiley-VCH GmbH Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/12/9

Y1 - 2020/12/9

N2 - The first adducts of NHCs (=N-heterocyclic carbenes) with aromatic polyphosphorus complexes are reported. The reactions of [Cp*Fe(η5-P5)] (1) (Cp*=pentamethyl-cyclopentadienyl) with IMe (=1,3,4,5-tetramethylimidazolin-2-ylidene), IMes (=1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene) and IDipp (=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) led to the corresponding neutral adducts which can be isolated in the solid state. However, in solution, they quickly undergo a dissociative equilibrium between the adduct and 1 including the corresponding NHC. The equilibrium is influenced by the bulkiness of the NHC. [Cp′′Ta(CO)2(η4-P4)] (Cp′′=1,3-di-tert-butylcyclopentadienyl) reacts with IMe under P atom abstraction to give an unprecedented cyclo-P3-containing anionic tantalum complex. DFT calculations shed light onto the energetics of the reaction pathways.

AB - The first adducts of NHCs (=N-heterocyclic carbenes) with aromatic polyphosphorus complexes are reported. The reactions of [Cp*Fe(η5-P5)] (1) (Cp*=pentamethyl-cyclopentadienyl) with IMe (=1,3,4,5-tetramethylimidazolin-2-ylidene), IMes (=1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene) and IDipp (=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene) led to the corresponding neutral adducts which can be isolated in the solid state. However, in solution, they quickly undergo a dissociative equilibrium between the adduct and 1 including the corresponding NHC. The equilibrium is influenced by the bulkiness of the NHC. [Cp′′Ta(CO)2(η4-P4)] (Cp′′=1,3-di-tert-butylcyclopentadienyl) reacts with IMe under P atom abstraction to give an unprecedented cyclo-P3-containing anionic tantalum complex. DFT calculations shed light onto the energetics of the reaction pathways.

KW - iron

KW - N-heterocyclic carbenes

KW - NMR spectroscopy

KW - nucleophilic attack

KW - phosphorus

KW - tantalum

KW - LIGANDS

KW - MOLECULE

KW - PENTAPHOSPHAFERROCENE

KW - COORDINATION

KW - N-HETEROCYCLIC CARBENES

UR - http://www.scopus.com/inward/record.url?scp=85094208457&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/871bf488-263a-3db8-beb7-3bb81409568e/

U2 - 10.1002/chem.202003393

DO - 10.1002/chem.202003393

M3 - Article

C2 - 32745336

AN - SCOPUS:85094208457

VL - 26

SP - 16251

EP - 16255

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 69

ER -