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<p>The reaction of diisobutyl ketone azine with phosphorus trichloride in acetonitrile occurs in two steps. The first step affords 2-(2,6-diniethylhept-3-en-4-yl)-5-isobutyl-4-isopropyl-2<i>H</i>-1,2,3-diazaphosphole (<b>2</b>). The subsequent reaction of this intermediate with PCl<sub>3</sub> gives 1,4-dichloro-3,6-diisobutyl-2,5-diisopropyl-1<i>H</i>,4<i>H</i>-3a,6a-diaza-1,4-diphosphapentalene (<b>3</b>) in 52% yield. The reduction of compound <b>3</b> with magnesium metal in THF produces 3,6-diisobutyl-2,5-diisopropyl-1<i>H</i>,4<i>H</i>-3a,6a-diaza-1,4-diphosphapentalene (<b>4</b>) in 57% yield. The complexation of <b>4</b> with an excess of CuCl affords the coordination polymer [<b>4</b>(CuCl)<sub>4</sub>]<sub><i>n</i></sub> (<b>5</b>), in which each phosphorus atom is coordinated to two copper atoms. In the presence of an excess of the ligand, the reaction gives [<b>4</b>(CuCl)<sub>2</sub>] (<b>6</b>).</p>

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3a,6a-Diaza-1,4-diphosphapentalene (DDP) as a tetratopic (κ2P, κ2P′) ligand. Synthesis of DDP bearing peripheral isobutyl and isopropyl substituents and its complexation with copper(i) chloride

  • 期刊论文

  • 发表日期：

    2025年12月1日

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  • N. V. Zolotareva,
  • V. V. Sushev,
  • M. D. Grishin,
  • R. V. Rumyantcev,
  • Yu. D. Timofeeva,
  • G. K. Fukin,
  • A. N. Kornev

摘要

The reaction of diisobutyl ketone azine with phosphorus trichloride in acetonitrile occurs in two steps. The first step affords 2-(2,6-diniethylhept-3-en-4-yl)-5-isobutyl-4-isopropyl-2H-1,2,3-diazaphosphole (2). The subsequent reaction of this intermediate with PCl3 gives 1,4-dichloro-3,6-diisobutyl-2,5-diisopropyl-1H,4H-3a,6a-diaza-1,4-diphosphapentalene (3) in 52% yield. The reduction of compound 3 with magnesium metal in THF produces 3,6-diisobutyl-2,5-diisopropyl-1H,4H-3a,6a-diaza-1,4-diphosphapentalene (4) in 57% yield. The complexation of 4 with an excess of CuCl affords the coordination polymer [4(CuCl)4]n (5), in which each phosphorus atom is coordinated to two copper atoms. In the presence of an excess of the ligand, the reaction gives [4(CuCl)2] (6).