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      Reversible Single-Electron-Transfer to Oxygen in a Stable N-Heterocyclic Carbene Palladium(I) Metalloradical

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          Abstract

          The chemical and electrochemical one-electron oxidation of [Pd(IPr) 2] ( 1) leads to the formation of mononuclear palladium(I) complex [Pd(IPr) 2][PF 6] ( 2). This bench-stable metalloradical has been fully characterized and its structure confirmed by X-ray diffraction analysis. EPR and DFT studies confirm the localization of the unpaired electron onto the metal center. Low temperature NMR and EPR measurements reveal the ability of complex 2 to reversibly coordinate and reduce the dioxygen molecule, leading to the formation of a three-coordinate complex, [Pd II(IPr) 2(η 1-O 2)] + ( 4), in which the unpaired electron has been transferred to the superoxido ligand.

          Abstract

          The synthesis and full characterization of the stable palladium(I) metalloradical [Pd(IPr) 2][PF 6] ( 2) is reported. The unpaired electron is located at the metal center according to the experimental (EPR) and theoretical (DFT) evidence. Complex 2 can reversibly bind and transfer an electron to a dioxygen molecule at a low temperature to form the tricoordinate palladium(II) superoxido complex [Pd(IPr) 2(η 1-O 2)] +.

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          EasySpin, a comprehensive software package for spectral simulation and analysis in EPR.

          Stefan Stoll, Arthur Schweiger (2006)
          EasySpin, a computational package for spectral simulation and analysis in EPR, is described. It is based on Matlab, a commercial technical computation software. EasySpin provides extensive EPR-related functionality, ranging from elementary spin physics to data analysis. In addition, it provides routines for the simulation of liquid- and solid-state EPR and ENDOR spectra. These simulation functions are built on a series of novel algorithms that enhance scope, speed and accuracy of spectral simulations. Spin systems with an arbitrary number of electron and nuclear spins are supported. The structure of the toolbox as well as the theoretical background underlying its simulation functionality are presented, and some illustrative examples are given.
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            Determination of N-Heterocyclic Carbene (NHC) Steric and Electronic Parameters using the [(NHC)Ir(CO)2Cl] System

            Carl D Hoff, Ivan Samardjiev, Hervé Clavier … (2008)
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              Steric and electronic properties of N-heterocyclic carbenes (NHC): a detailed study on their interaction with Ni(CO)4.

              Reto Dorta, Edwin Stevens, Natalie Scott … (2005)
              N-heterocyclic carbene ligands IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5) react with Ni(CO)(4) to give the saturated tricarbonyl complexes Ni(CO)(3)(IMes) (8), Ni(CO)(3)(SIMes) (9), Ni(CO)(3)(IPr) (10), Ni(CO)(3)(SIPr) (11), and Ni(CO)(3)(ICy) (12), respectively. The electronic properties of these complexes have been compared to their phosphine analogues of general formula Ni(CO)(3)(PR(3)) by recording their nu(CO) stretching frequencies. While all of these NHCs are better donors than tertiary phosphines, the differences in donor properties between ligands 1-5 are surprisingly small. Novel, unsaturated Ni(CO)(2)(IAd) (13) and Ni(CO)(2)(I(t)()Bu) (14) compounds are obtained from the reaction of Ni(CO)(4) with IAd (6) and I(t)()Bu (7). Complexes 13 and 14 are highly active toward substitution of the NHC as well as the carbonyl ligands. This has allowed the determination of Ni-C(NHC) bond dissociation energies and the synthesis of various unsaturated Ni(0) and Ni(II) complexes. Computational studies on compounds 8-14 are in line with the experimental findings and show that IAd (6) and I(t)()Bu (7) are more bulky than IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5). Furthermore, a method based on %V(bur) values has been developed for the direct comparison of steric requirements of NHCs and tertiary phosphines. Complexes 8-14, as well as NiCl(C(3)H(5))(I(t)()Bu) (16) and NiBr(C(3)H(5))(I(t)()Bu) (17), have been characterized by X-ray crystallography.
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                Author and article information

                Journal
                Journal ID (nlm-ta): Inorg Chem
                Journal ID (iso-abbrev): Inorg Chem
                Journal ID (publisher-id): ic
                Journal ID (coden): inocaj
                Title: Inorganic Chemistry
                Publisher: American Chemical Society
                ISSN (Print): 0020-1669
                ISSN (Electronic): 1520-510X
                Publication date (Electronic): 22 November 2023
                Publication date Collection: 11 December 2023
                Volume: 62
                Issue: 49
                Pages: 19838-19842
                Affiliations
                Departamento de Química Orgánica y Química Inorgánica, Instituto de Investigación Química “Andrés M. del Río”, Universidad de Alcalá, Campus Universitario , 28805 Alcalá de Henares, Madrid, Spain
                Author notes
                Author information
                https://orcid.org/0000-0002-7411-4524
                https://orcid.org/0000-0002-9279-210X
                https://orcid.org/0000-0002-5545-5112
                https://orcid.org/0000-0002-6215-8116
                https://orcid.org/0000-0001-8101-1358
                Article
                DOI: 10.1021/acs.inorgchem.3c02878
                PMC ID: 10716904
                PubMed ID: 37992293
                SO-VID: 0121ae34-492d-4561-bd5c-3a82a8c54c38
                Copyright © © 2023 The Authors. Published by American Chemical Society
                License:

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                Date received : 17 August 2023
                Date accepted : 20 November 2023
                Date revision received : 19 November 2023
                Funding
                Funded by: Ministerio de Ciencia e Innovación, doi 10.13039/501100004837;
                Award ID: PID2020-114637GB-I00
                Funded by: Universidad de Alcalá, doi 10.13039/501100006302;
                Award ID: NA
                Categories
                Subject: Communication
                Custom metadata
                document-id-old-9 ic3c02878
                document-id-new-14 ic3c02878
                ccc-price

                ScienceOpen disciplines: Inorganic & Bioinorganic chemistry
                Data availability:
                ScienceOpen disciplines: Inorganic & Bioinorganic chemistry

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