二碘 (I2) 与钳形复合物 [2,6-bis{(Me2NCH2)2}C6H3]PtIII 所形成平衡的计算研究：使用 "Pt-I2"、"Pt-I--I2 "和 "C para--I2 "物种的 I2 分子内流动性

IF 2 4区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

European Journal of Inorganic Chemistry Pub Date : 2024-06-04 DOI:10.1002/ejic.202400242

Prof. Allan J. Canty, Prof. Gerard van Koten

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引用次数: 0

摘要

DFT 计算表明，当二碘与二氯甲烷中的方形平面铂(II)钳形复合物 Pt(NCN)I（NCN = [2,6-双{(二甲基氨基)甲基}苯基-N,C,N]-）相互作用时，存在壁垒极低的平衡。存在的物种包括方形平面的 Pt(NCN)(η1-I3)和方形金字塔形的 Pt(NCN)I(η1-I2)，它们通过 I2 桥接 Pt-I 键的三角转换态相互转化，以及二碘在炔环的对位与 Pt(NCN)I(η1-I2)的相互作用，它们通过二碘桥接 Cortho 和 Cmeta 位置的转换态相互转化。在 Pt:I2 摩尔比为 1:2 的模型体系中，也发生了类似的分子内重排，出现了 Pt(NCN)(η1-I3)(η1-I2)等物种以及二碘在 (钳形) PtI 平面上的流动性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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

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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.

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来源期刊

European Journal of Inorganic Chemistry 化学-无机化学与核化学

CiteScore

4.30

自引率

4.30%

发文量

419

审稿时长

1.3 months

期刊介绍： The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.