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Synthesis of Complexes with Protic NH,NH-NHC Ligands via Oxidative Addition of 2-Halogenoazoles to Zero-Valent Transition Metals

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† Institut für Anorganische und Analytische Chemie and NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstrasse 30, D-48149 Münster, Germany
‡ Organisch-Chemisches Institut, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, D-48149 Münster, Germany
*E-mail: [email protected]
Cite this: Organometallics 2014, 33, 23, 6975–6987
Publication Date (Web):November 21, 2014
https://doi.org/10.1021/om501120u
Copyright © 2014 American Chemical Society
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    Abstract

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    A versatile, one-pot synthesis for the preparation of transition metal complexes bearing protic NH,NH-NHC ligands is disclosed. The reaction of unsubstituted 2-halogenoazoles with zerovalent metal complexes of the type [M(PPh3)4] (M = Pd, Pt) in the presence of NH4BF4 proceeds by oxidative addition of the C2–X (X = Cl, Br, I) bond to the transition metal followed by protonation at the ring nitrogen atom, leading to complexes of the type trans-[MX(PPh3)2(NH,NH-NHC)] (M = PdII, PtII; NHC = benzimidazolylidene or imidazolylidene). The trans-complexes have been obtained in all cases. The time needed to complete the reaction depends on the halogen present in the azole, and the rate of the oxidative addition follows the order C2–I > C2–Br > C2–Cl. The N–H groups of the coordinated NH,NH-NHC have been deprotonated followed by reaction with MeI to give the NMe,NMe-substituted classical NHC ligands. The N–H groups of the protic NHCs are hydrogen bond donors. The formation of N–H···O hydrogen bonds has been observed via 1H NMR spectroscopy upon titration of the complexes bearing protic NHCs with DMPU.

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    NMR and mass spectra for all new compounds and crystallographic information files (CIFs) for trans-[3]BF4, trans-[5]BF4·CH2Cl2, trans-[6]BF4·CH2Cl2, trans-[8]BF4·CH2Cl2, trans-[13]BF4·CH2Cl2, and trans-[14]BF4·CH2Cl2 as well as data concerning the titration experiments with DMPU. Crystallographic data for trans-[2]BF4·C4H8O and trans-[11]BF4·CH2Cl2 have previously been deposited with the Cambridge Crystallographic Data Centre (CCDC numbers 962104 and 962105). (25) This material is available free of charge via the Internet at http://pubs.acs.org.

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