{(mesitylene)W(CO)3P(OBu)3}(2+) | 133947-43-0

• 英文名称: {(mesitylene)W(CO)3P(OBu)3}(2+)
• CAS: 133947-43-0
• 化学式: C₂₄H₃₉O₆PW
• 分子量: 638.394
• InChiKey: FHDVATZKGCVPDM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  {(mesitylene)W(CO)3P(OBu)3}(2+) 以 乙腈 为溶剂， 生成 tricarbonyl-tris(acetonitrile)tungsten(0) 、 均三甲苯
  参考文献：
  名称：

  Reactivity of 17-, 18-, and 19-electron cationic complexes generated by the electrochemical oxidation of tricarbonyl(mesitylene)tungsten

  摘要：

  The electrochemical oxidation of (mesitylene) W(CO)3 (W) in MeCN produces the 17-electron complex W+, which reacts very rapidly with solvent (S) or tri-n-butyl phosphite (P) to give 19-electron species (WS+, WP+) that undergo spontaneous further oxidation to the 18-electron analogues (WS2+, WP2+). The identities of WS2+ were established by voltammetric, IR spectroelectrochemical, and NMR experiments. Although the 17-electron half arrow pointing to the right and to the left 19-electron transformation is not directly observable, digital simulation techniques allowed selection of a probable mechanism and semiquantitative determination of the rate and equilibrium parameters describing the interconversion of the 17-, 18-, and 19-electron species: W+ + S half arrow pointing to the right and to the left WS+, k congruent-to 10(5) M-1 s-1, K(eq) congruent-to 10(-1) M-1; W+ + P half arrow pointing to the right and to the left WP+, k congruent-to 10(7) M-14 s-1 K(eq) congruent-to 3 X 10(3) M-1 at 298 K. The related 18-electron complex WS2+ is quite reactive, but orders of magnitude less so than W+ and WS+. Experiments with (mesitylene) Cr(CO)3 (Cr) suggest that associative attack by MeCN at the 17-electron Cr+ is 10(4) times slower than attack at the W+ analogue. This study illustrates the power of digital simulation techniques for interpreting complex mechanistic schemes and characterizing important but unobservable reaction intermediates. Electrochemical oxidation of (arene) W(CO)3 occurs without loss of arene or CO ligands, suggesting that the electroactivation of these complexes may have useful synthetic applications; this contrasts sharply with (arene) Cr(CO)3 analogues, which decompose with loss of arene and CO ligands upon oxidation in MeCN.

  DOI：

  10.1021/ja00011a002
• 作为产物：
  描述：

  三羰基三甲基苯钨 、 三丁基,三丁酯 以 乙腈 为溶剂， 生成 {(mesitylene)W(CO)3P(OBu)3}(2+)
  参考文献：
  名称：

  Reactivity of 17-, 18-, and 19-electron cationic complexes generated by the electrochemical oxidation of tricarbonyl(mesitylene)tungsten

  摘要：

  The electrochemical oxidation of (mesitylene) W(CO)3 (W) in MeCN produces the 17-electron complex W+, which reacts very rapidly with solvent (S) or tri-n-butyl phosphite (P) to give 19-electron species (WS+, WP+) that undergo spontaneous further oxidation to the 18-electron analogues (WS2+, WP2+). The identities of WS2+ were established by voltammetric, IR spectroelectrochemical, and NMR experiments. Although the 17-electron half arrow pointing to the right and to the left 19-electron transformation is not directly observable, digital simulation techniques allowed selection of a probable mechanism and semiquantitative determination of the rate and equilibrium parameters describing the interconversion of the 17-, 18-, and 19-electron species: W+ + S half arrow pointing to the right and to the left WS+, k congruent-to 10(5) M-1 s-1, K(eq) congruent-to 10(-1) M-1; W+ + P half arrow pointing to the right and to the left WP+, k congruent-to 10(7) M-14 s-1 K(eq) congruent-to 3 X 10(3) M-1 at 298 K. The related 18-electron complex WS2+ is quite reactive, but orders of magnitude less so than W+ and WS+. Experiments with (mesitylene) Cr(CO)3 (Cr) suggest that associative attack by MeCN at the 17-electron Cr+ is 10(4) times slower than attack at the W+ analogue. This study illustrates the power of digital simulation techniques for interpreting complex mechanistic schemes and characterizing important but unobservable reaction intermediates. Electrochemical oxidation of (arene) W(CO)3 occurs without loss of arene or CO ligands, suggesting that the electroactivation of these complexes may have useful synthetic applications; this contrasts sharply with (arene) Cr(CO)3 analogues, which decompose with loss of arene and CO ligands upon oxidation in MeCN.

  DOI：

  10.1021/ja00011a002