Computational Study of Equilibria Formed by Diiodine (I2) and the Pincer Complex [2,6-bis{(Me2NCH2)2}C6H3]PtIII: Intramolecular Mobility of I2 Using ′Pt-I2′, ′Pt-I ⋅ ⋅ ⋅ I2′ and ′Cpara ⋅ ⋅ ⋅ I2′ Species

Allan J. Canty; Gerard van Koten

doi:10.1002/ejic.202400242

Computational Study of Equilibria Formed by Diiodine (I2) and the Pincer Complex [2,6-bis{(Me2NCH2)2}C6H3]PtIII: Intramolecular Mobility of I2 Using ′Pt-I2′, ′Pt-I ⋅ ⋅ ⋅ I2′ and ′Cpara ⋅ ⋅ ⋅ I2′ Species

Allan J. Canty, Gerard van Koten

University of Tasmania

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

DFT computation indicates the presence of solution equilibria with very low barriers when diiodine interacts with the square-planar platinum(II) pincer complex Pt(NCN)I (NCN=[2,6-bis{(dimethylamino)methyl}phenyl-N,C,N]⁻) in dichloromethane. Species present include square-planar Pt(NCN)(η¹-I₃) and square-pyramidal Pt(NCN)I(η¹-I₂) interconverted via a triangular transition state with I₂ bridging a Pt−I bond, and interaction of diiodine at the para-position of the arene ring interconverted with Pt(NCN)I(η¹-I₂) via a transition state with diiodine bridging the C_ortho- and C_meta-positions. Similar facile intramolecular rearrangements occur for a model system with a molar ratio of 1 : 2 for Pt : I₂, exhibiting species such as Pt(NCN)(η¹-I₃)(η¹-I₂) and mobility of diiodine over the (pincer)PtI plane.

Original language	English
Article number	e202400242
Number of pages	6
Journal	European Journal of Inorganic Chemistry
Volume	27
Issue number	26
Early online date	4 Jun 2024
DOIs	https://doi.org/10.1002/ejic.202400242
Publication status	Published - 11 Sept 2024

Bibliographical note

Publisher Copyright:
© 2024 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.

Funding

We acknowledge support from the Australian National Computing Infrastructure and the University of Tasmania. Open Access publishing facilitated by University of Tasmania, as part of the Wiley \u2010 University of Tasmania agreement via the Council of Australian University Librarians.

Funders	Funder number
University of Tasmania

Keywords

DFT organoplatinum
diiodine organometallic
fluxional molecules
organometallic equilibria
pincer complexes

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Canty, A. J., & van Koten, G. (2024). Computational Study of Equilibria Formed by Diiodine (I2) and the Pincer Complex [2,6-bis{(Me2NCH2)2}C6H3]PtIII: Intramolecular Mobility of I2 Using ′Pt-I2′, ′Pt-I ⋅ ⋅ ⋅ I2′ and ′Cpara ⋅ ⋅ ⋅ I2′ Species. European Journal of Inorganic Chemistry, 27(26), Article e202400242. https://doi.org/10.1002/ejic.202400242

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title = "Computational Study of Equilibria Formed by Diiodine (I2) and the Pincer Complex [2,6-bis\{(Me2NCH2)2\}C6H3]PtIII: Intramolecular Mobility of I2 Using ′Pt-I2′, ′Pt-I ⋅ ⋅ ⋅ I2′ and ′Cpara ⋅ ⋅ ⋅ I2′ Species",

abstract = "DFT computation indicates the presence of solution equilibria with very low barriers when diiodine interacts with the square-planar platinum(II) pincer complex Pt(NCN)I (NCN=[2,6-bis\{(dimethylamino)methyl\}phenyl-N,C,N]−) in dichloromethane. Species present include square-planar Pt(NCN)(η1-I3) and square-pyramidal Pt(NCN)I(η1-I2) interconverted via a triangular transition state with I2 bridging a Pt−I bond, and interaction of diiodine at the para-position of the arene ring interconverted with Pt(NCN)I(η1-I2) via a transition state with diiodine bridging the Cortho- and Cmeta-positions. Similar facile intramolecular rearrangements occur for a model system with a molar ratio of 1 : 2 for Pt : I2, exhibiting species such as Pt(NCN)(η1-I3)(η1-I2) and mobility of diiodine over the (pincer)PtI plane.",

keywords = "DFT organoplatinum, diiodine organometallic, fluxional molecules, organometallic equilibria, pincer complexes",

author = "Canty, \{Allan J.\} and \{van Koten\}, Gerard",

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Canty, AJ & van Koten, G 2024, 'Computational Study of Equilibria Formed by Diiodine (I2) and the Pincer Complex [2,6-bis{(Me2NCH2)2}C6H3]PtIII: Intramolecular Mobility of I2 Using ′Pt-I2′, ′Pt-I ⋅ ⋅ ⋅ I2′ and ′Cpara ⋅ ⋅ ⋅ I2′ Species', European Journal of Inorganic Chemistry, vol. 27, no. 26, e202400242. https://doi.org/10.1002/ejic.202400242

Computational Study of Equilibria Formed by Diiodine (I2) and the Pincer Complex [2,6-bis{(Me2NCH2)2}C6H3]PtIII: Intramolecular Mobility of I2 Using ′Pt-I2′, ′Pt-I ⋅ ⋅ ⋅ I2′ and ′Cpara ⋅ ⋅ ⋅ I2′ Species. / Canty, Allan J.; van Koten, Gerard.
In: European Journal of Inorganic Chemistry, Vol. 27, No. 26, e202400242, 11.09.2024.

Research output: Contribution to journal › Article › Academic › peer-review

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AB - DFT computation indicates the presence of solution equilibria with very low barriers when diiodine interacts with the square-planar platinum(II) pincer complex Pt(NCN)I (NCN=[2,6-bis{(dimethylamino)methyl}phenyl-N,C,N]−) in dichloromethane. Species present include square-planar Pt(NCN)(η1-I3) and square-pyramidal Pt(NCN)I(η1-I2) interconverted via a triangular transition state with I2 bridging a Pt−I bond, and interaction of diiodine at the para-position of the arene ring interconverted with Pt(NCN)I(η1-I2) via a transition state with diiodine bridging the Cortho- and Cmeta-positions. Similar facile intramolecular rearrangements occur for a model system with a molar ratio of 1 : 2 for Pt : I2, exhibiting species such as Pt(NCN)(η1-I3)(η1-I2) and mobility of diiodine over the (pincer)PtI plane.

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KW - organometallic equilibria

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Canty AJ, van Koten G. Computational Study of Equilibria Formed by Diiodine (I2) and the Pincer Complex [2,6-bis{(Me2NCH2)2}C6H3]PtIII: Intramolecular Mobility of I2 Using ′Pt-I2′, ′Pt-I ⋅ ⋅ ⋅ I2′ and ′Cpara ⋅ ⋅ ⋅ I2′ Species. European Journal of Inorganic Chemistry. 2024 Sept 11;27(26):e202400242. Epub 2024 Jun 4. doi: 10.1002/ejic.202400242