Catalytic C(sp2)–C(sp3) Cross-Electrophile Coupling in the PtII–NaI–С2Н3I–СН3I–Acetone System

IF 1.3 4区化学 Q4 CHEMISTRY, PHYSICAL

Kinetics and Catalysis Pub Date : 2024-04-27 DOI:10.1134/S002315842401004X

T. V. Krasnyakova, D. V. Nikitenko, S. A. Mitchenko

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Abstract

A new catalytic system for reductive С(sp²)–C(sp³) cross-electrophile coupling was designed: Pt^II iodide complexes in an acetone solution of NaI catalyze the coupling of methyl iodide with vinyl iodide to form propylene. Simultaneously, a small amount of 1,3-butadiene, the product of C(sp²)–C(sp²) coupling, is released. The total yield of the products with respect to the reacted vinyl iodide is almost quantitative. In a large excess of CH₃I, the C₂H₃I consumption is described by the pseudo-first-order kinetics. The cross-coupling occurs as the following sequence of steps: oxidative addition of CH₃I to Pt^II iodide complexes to form a methyl Pt^IV complex → reduction of the methyl Pt^IV complex with I^– to form the corresponding Pt^II derivative → oxidative addition of C₂H₃I to the Pt^II derivative → reductive elimination of organyl ligands from the intermediate methyl vinyl Pt^IV complex.

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PtII-NaI-С2Н3I-СН3I-Acetone 体系中的催化 C(sp2)-C(sp3)交电偶联

摘要设计了一种用于还原С(sp2)-C(sp3)交叉亲电偶联的新催化体系：在 NaI 的丙酮溶液中的 PtII 碘化物络合物可催化甲基碘与乙烯基碘偶联生成丙烯。与此同时，C(sp2)-C(sp2)偶联的产物--少量 1,3-丁二烯也被释放出来。与反应后的碘化乙烯相比，产物的总收率几乎是定量的。在大量过量 CH3I 的情况下，C2H3I 的消耗量用伪一阶动力学来描述。交叉偶联按以下步骤顺序进行：CH3I 与 PtII 碘化物络合物氧化加成，形成 PtIV 甲基络合物 → I- 还原 PtIV 甲基络合物，形成相应的 PtII 衍生物 → C2H3I 与 PtII 衍生物氧化加成 → 从 PtIV 甲基乙烯基络合物中间还原消除羰基配体。

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来源期刊

Kinetics and Catalysis 化学-物理化学

CiteScore

2.10

自引率

27.30%

发文量

审稿时长

6-12 weeks

期刊介绍： Kinetics and Catalysis Russian is a periodical that publishes theoretical and experimental works on homogeneous and heterogeneous kinetics and catalysis. Other topics include the mechanism and kinetics of noncatalytic processes in gaseous, liquid, and solid phases, quantum chemical calculations in kinetics and catalysis, methods of studying catalytic processes and catalysts, the chemistry of catalysts and adsorbent surfaces, the structure and physicochemical properties of catalysts, preparation and poisoning of catalysts, macrokinetics, and computer simulations in catalysis. The journal also publishes review articles on contemporary problems in kinetics and catalysis. The journal welcomes manuscripts from all countries in the English or Russian language.