Anionic Cyclometalated Platinum(II) Tetrazolato Complexes as Viable Photoredox Catalysts

Anna Maria Ranieri, Liam K. Burt, Stefano Stagni, Stefano Zacchini, Brian W. Skelton, Mark I. Ogden, Alex C. Bissember, Massimiliano Massi

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The synthesis, characterization, photophysical and photocatalytic studies of anionic platinum(II) tetrazolato complexes, with the general structure [TBA][Pt(CNC)TzR], are reported, where CNC 2- represents a doubly cyclometalated 2,4,6-triphenylpyridine, TzR - is an anionic 5-substituted tetrazolato ligand (with a variable R functional group), and TBA + is the tetrabutylammonium countercation. The complexes were prepared by substitution of the DMSO ligand in [Pt(CNC)(DMSO)] with the corresponding tetrazolato ligand. No emission from the platinum(II) complexes was detected at room temperature in solution, but the photophysical properties could be assessed in the solid state, where all the complexes display emission bands attributed to aggregates. The platinum(II) complexes were found to facilitate a range of fundamental classes of visible-light-mediated photoredox-catalyzed reactions, including α-amino C-H functionalization processes, such as Povarov-type reactions and the addition of α-amino C-H bonds across Michael acceptors, in addition to ATRA chemistry, and a hydrodeiodination. With the exception of the hydrodeiodination process, the best Pt(II) catalysts provided turnover numbers of 150-175 in each of these transformations.

Original languageEnglish
Pages (from-to)1108-1117
Number of pages10
JournalOrganometallics
Volume38
Issue number5
DOIs
Publication statusPublished - 11 Mar 2019

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Platinum
platinum
Ligands
Dimethyl Sulfoxide
catalysts
ligands
Catalysts
Functional groups
Substitution reactions
substitutes
chemistry
solid state
room temperature
synthesis
Temperature

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Ranieri, A. M., Burt, L. K., Stagni, S., Zacchini, S., Skelton, B. W., Ogden, M. I., ... Massi, M. (2019). Anionic Cyclometalated Platinum(II) Tetrazolato Complexes as Viable Photoredox Catalysts. Organometallics, 38(5), 1108-1117. https://doi.org/10.1021/acs.organomet.8b00913
Ranieri, Anna Maria ; Burt, Liam K. ; Stagni, Stefano ; Zacchini, Stefano ; Skelton, Brian W. ; Ogden, Mark I. ; Bissember, Alex C. ; Massi, Massimiliano. / Anionic Cyclometalated Platinum(II) Tetrazolato Complexes as Viable Photoredox Catalysts. In: Organometallics. 2019 ; Vol. 38, No. 5. pp. 1108-1117.
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Ranieri, AM, Burt, LK, Stagni, S, Zacchini, S, Skelton, BW, Ogden, MI, Bissember, AC & Massi, M 2019, 'Anionic Cyclometalated Platinum(II) Tetrazolato Complexes as Viable Photoredox Catalysts' Organometallics, vol. 38, no. 5, pp. 1108-1117. https://doi.org/10.1021/acs.organomet.8b00913

Anionic Cyclometalated Platinum(II) Tetrazolato Complexes as Viable Photoredox Catalysts. / Ranieri, Anna Maria; Burt, Liam K.; Stagni, Stefano; Zacchini, Stefano; Skelton, Brian W.; Ogden, Mark I.; Bissember, Alex C.; Massi, Massimiliano.

In: Organometallics, Vol. 38, No. 5, 11.03.2019, p. 1108-1117.

Research output: Contribution to journalArticle

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T1 - Anionic Cyclometalated Platinum(II) Tetrazolato Complexes as Viable Photoredox Catalysts

AU - Ranieri, Anna Maria

AU - Burt, Liam K.

AU - Stagni, Stefano

AU - Zacchini, Stefano

AU - Skelton, Brian W.

AU - Ogden, Mark I.

AU - Bissember, Alex C.

AU - Massi, Massimiliano

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N2 - The synthesis, characterization, photophysical and photocatalytic studies of anionic platinum(II) tetrazolato complexes, with the general structure [TBA][Pt(CNC)TzR], are reported, where CNC 2- represents a doubly cyclometalated 2,4,6-triphenylpyridine, TzR - is an anionic 5-substituted tetrazolato ligand (with a variable R functional group), and TBA + is the tetrabutylammonium countercation. The complexes were prepared by substitution of the DMSO ligand in [Pt(CNC)(DMSO)] with the corresponding tetrazolato ligand. No emission from the platinum(II) complexes was detected at room temperature in solution, but the photophysical properties could be assessed in the solid state, where all the complexes display emission bands attributed to aggregates. The platinum(II) complexes were found to facilitate a range of fundamental classes of visible-light-mediated photoredox-catalyzed reactions, including α-amino C-H functionalization processes, such as Povarov-type reactions and the addition of α-amino C-H bonds across Michael acceptors, in addition to ATRA chemistry, and a hydrodeiodination. With the exception of the hydrodeiodination process, the best Pt(II) catalysts provided turnover numbers of 150-175 in each of these transformations.

AB - The synthesis, characterization, photophysical and photocatalytic studies of anionic platinum(II) tetrazolato complexes, with the general structure [TBA][Pt(CNC)TzR], are reported, where CNC 2- represents a doubly cyclometalated 2,4,6-triphenylpyridine, TzR - is an anionic 5-substituted tetrazolato ligand (with a variable R functional group), and TBA + is the tetrabutylammonium countercation. The complexes were prepared by substitution of the DMSO ligand in [Pt(CNC)(DMSO)] with the corresponding tetrazolato ligand. No emission from the platinum(II) complexes was detected at room temperature in solution, but the photophysical properties could be assessed in the solid state, where all the complexes display emission bands attributed to aggregates. The platinum(II) complexes were found to facilitate a range of fundamental classes of visible-light-mediated photoredox-catalyzed reactions, including α-amino C-H functionalization processes, such as Povarov-type reactions and the addition of α-amino C-H bonds across Michael acceptors, in addition to ATRA chemistry, and a hydrodeiodination. With the exception of the hydrodeiodination process, the best Pt(II) catalysts provided turnover numbers of 150-175 in each of these transformations.

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