Comparing the Ligand Behavior of N-Heterocyclic Phosphenium and Nitrosyl Units in Iron and Chromium Complexes

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dc.contributor University of Helsinki, Department of Chemistry en
dc.contributor.author Feil, Christoph M.
dc.contributor.author Hettich, Thomas D.
dc.contributor.author Beyer, Katharina
dc.contributor.author Sondermann, Christina
dc.contributor.author Schlindwein, Simon H.
dc.contributor.author Nieger, Martin
dc.contributor.author Gudat, Dietrich
dc.date.accessioned 2021-01-18T14:50:00Z
dc.date.available 2021-01-18T14:50:00Z
dc.date.issued 2019-05-06
dc.identifier.citation Feil , C M , Hettich , T D , Beyer , K , Sondermann , C , Schlindwein , S H , Nieger , M & Gudat , D 2019 , ' Comparing the Ligand Behavior of N-Heterocyclic Phosphenium and Nitrosyl Units in Iron and Chromium Complexes ' , Inorganic Chemistry , vol. 58 , no. 9 , pp. 6517-6528 . https://doi.org/10.1021/acs.inorgchem.9b00737 en
dc.identifier.issn 0020-1669
dc.identifier.other PURE: 125013163
dc.identifier.other PURE UUID: 7bba1bda-628c-44d1-a9b9-d61fce741a59
dc.identifier.other WOS: 000467351100123
dc.identifier.other ORCID: /0000-0003-1677-0109/work/58507923
dc.identifier.uri http://hdl.handle.net/10138/324824
dc.description.abstract N-Heterocyclic phosphenium (NHP) and nitro-sonium (NO+) ligands are often viewed as isolobal analogues that share the capability to switch between different charge states and thus display redox "noninnocent" behavior. We report here on mixed complexes [(NHP)M(CO)(n)(NO)] (M = Fe, Cr; n = 2, 3), which permit evaluating the donor/acceptor properties of both types of ligands and their interplay in a single complex. The crystalline target compounds were obtained from reactions of N-heterocyclic phosphenium triflates with PPN[Fe(CO)(3)(NO)] or PPN[Cr(CO)(4)-(NO)], respectively, and fully characterized (PPN = nitride-bistriphenylphosphonium cation). The structural and spectroscopic (IR, UV-vis) data support the presence of carbene-analogue NHP ligands with an overall positive charge state and pi-acceptor character. Even if the structural features of the M-NO unit were in all but one product blurred by crystallographic CO/NO disorder, spectroscopic studies and the structural data of the remaining compound suggest that the NO units exhibit nitroxide (NO-) character. This assignment was validated by computational studies, which reveal also that the electronic structure of iron NHP/ NO complexes is closely akin to that of the Hieber anion, [Fe(CO)(3)(NO)](-). The electrophilic character of the NHP units is further reflected in the chemical behavior of the mixed complexes. Cyclic voltammetry and IR-SEC studies revealed that complex [(NHP)Fe(CO)(2) (NO)] (4) undergoes chemically reversible one-electron reduction. Computational studies indicate that the NHP unit in the resulting product carries significant radical character, and the reduction may thus be classified as predominantly ligand-centered. Reaction of 4 with sodium azide proceeded likewise under nucleophilic attack at phosphorus and decomplexation, while super hydride and methyl lithium reacted with all chromium and iron complexes via transfer of a hydride or methyl anion to the NHP unit to afford anionic phosphine complexes. Some of these species were isolated after cation exchange or trapped with electrophiles (H+, SnPh3(+)) to afford neutral complexes representing the products of a formal hydrogenation or hydrostannylation of the original M=P double bond. en
dc.format.extent 12
dc.language.iso eng
dc.relation.ispartof Inorganic Chemistry
dc.rights en
dc.subject METAL-COMPLEXES en
dc.subject REACTIVITY en
dc.subject CHEMISTRY en
dc.subject ANALOGS en
dc.subject IONS en
dc.subject 116 Chemical sciences en
dc.title Comparing the Ligand Behavior of N-Heterocyclic Phosphenium and Nitrosyl Units in Iron and Chromium Complexes en
dc.type Article
dc.description.version Peer reviewed
dc.identifier.doi https://doi.org/10.1021/acs.inorgchem.9b00737
dc.type.uri info:eu-repo/semantics/other
dc.type.uri info:eu-repo/semantics/acceptedVersion
dc.contributor.pbl

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