Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes

An important factor in obtaining reversible multi-electron transfer is overcoming large changes in coordination geometry. One strategy is to use ligands that can support the geometries favored before and after the electron transfer. Pip(2)NCN(−) pincer and terpyridine ligands are used to support squ...

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Autores principales: Kuyuldar, Seher, Burda, Clemens, Connick, William B.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9066165/
https://www.ncbi.nlm.nih.gov/pubmed/35521348
http://dx.doi.org/10.1039/c9ra03939b
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author Kuyuldar, Seher
Burda, Clemens
Connick, William B.
author_facet Kuyuldar, Seher
Burda, Clemens
Connick, William B.
author_sort Kuyuldar, Seher
collection PubMed
description An important factor in obtaining reversible multi-electron transfer is overcoming large changes in coordination geometry. One strategy is to use ligands that can support the geometries favored before and after the electron transfer. Pip(2)NCN(−) pincer and terpyridine ligands are used to support square planar Pt(ii) and octahedral Pt(iv). For the Pt(ii) complexes, [Pt(Z-pip(2)NCN)(R-tpy)](+) (Z = NO(2), MeO, H; R = H, tertyl butyl, tolyl), (1)H NMR spectroscopy shows that the Z-pip(2)NCN(−) ligand is monodentate whereas the R-terpyridyl ligand is tridentate. The availability of flanking piperidyl groups of the monodentate pincer ligand is essential for the stabilization of the metal center upon oxidation. Pt(Z-pip(2)NCN)(R-tpy)(+) complexes undergo two-electron platinum centered oxidation near 0.4 V and two Pt(tpy) centered reductions near −1.0 V and −1.5 V. An estimate of n(ox)/n(red) = 1.8 is consistent with an oxidation that involves two-electron transfer per Pt center. Variation in the pincer-(Z) and terpyridine-(R) substituents allows for tuning of the oxidation process over a 260 mV range and the two reduction processes over ranges of 230 mV (first reduction) and 290 mV (second reduction step).
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spelling pubmed-90661652022-05-04 Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes Kuyuldar, Seher Burda, Clemens Connick, William B. RSC Adv Chemistry An important factor in obtaining reversible multi-electron transfer is overcoming large changes in coordination geometry. One strategy is to use ligands that can support the geometries favored before and after the electron transfer. Pip(2)NCN(−) pincer and terpyridine ligands are used to support square planar Pt(ii) and octahedral Pt(iv). For the Pt(ii) complexes, [Pt(Z-pip(2)NCN)(R-tpy)](+) (Z = NO(2), MeO, H; R = H, tertyl butyl, tolyl), (1)H NMR spectroscopy shows that the Z-pip(2)NCN(−) ligand is monodentate whereas the R-terpyridyl ligand is tridentate. The availability of flanking piperidyl groups of the monodentate pincer ligand is essential for the stabilization of the metal center upon oxidation. Pt(Z-pip(2)NCN)(R-tpy)(+) complexes undergo two-electron platinum centered oxidation near 0.4 V and two Pt(tpy) centered reductions near −1.0 V and −1.5 V. An estimate of n(ox)/n(red) = 1.8 is consistent with an oxidation that involves two-electron transfer per Pt center. Variation in the pincer-(Z) and terpyridine-(R) substituents allows for tuning of the oxidation process over a 260 mV range and the two reduction processes over ranges of 230 mV (first reduction) and 290 mV (second reduction step). The Royal Society of Chemistry 2019-07-05 /pmc/articles/PMC9066165/ /pubmed/35521348 http://dx.doi.org/10.1039/c9ra03939b Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Kuyuldar, Seher
Burda, Clemens
Connick, William B.
Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes
title Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes
title_full Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes
title_fullStr Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes
title_full_unstemmed Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes
title_short Tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes
title_sort tuning two-electron transfer in terpyridine-based platinum(ii) pincer complexes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9066165/
https://www.ncbi.nlm.nih.gov/pubmed/35521348
http://dx.doi.org/10.1039/c9ra03939b
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