bis(triphenylarsine)(methyleneoxy-1,2-phenylene)palladium | 186395-02-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(triphenylarsine)(methyleneoxy-1,2-phenylene)palladium
• CAS: 186395-02-8
• 化学式: C₄₃H₃₆As₂OPd
• 分子量: 825.021
• InChiKey: RDBURUFOOJINOA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  trans-bis(triphenylarsine)[2-(dimethylphenylsilylmethoxy)phenyl]iodopalladium 在 potassium fluoride 、 cesium fluoride 作用下， 以 乙腈 为溶剂， 生成 bis(triphenylarsine)(methyleneoxy-1,2-phenylene)palladium
  参考文献：
  名称：

  芳基钯（II）和芳基铂（II）与硅烷和锡烷的配合物的分子内金属转移

  摘要：

  o-（Me 2 RSiCH 2 O）C 6 H 4 I（R = Me，Ph，F）的氧化加成至钯（0）络合物[Pd（PPh 3）]，[Pd（dba）（AsPh 3）2 ]（dba =二亚苄基丙酮）和[Pd（dba）（L 2）] [L 2 = 1,1'-双（二苯基膦基）二茂铁（dppf），2,2'-联吡啶（bpy），邻-邻菲咯啉（phen）]生成相应的络合物o-（Me 2 RCH 2 O）C 6 H 4 Pd（L 2）I（L = PPh 3，AsPh 3 ; L2 = dppf，bpy，phen）。这种Pd（II）/ Si过渡金属化是Hiyama交叉偶联反应的关键步骤，可在不同的氟化物作为促进剂的情况下平稳地进行。另外，碳酸银和碳酸钾可能通过形成具有Pd-O键的中间体来促进金属转移。相关的Pt（II）/ Sn和Pt（II）/ Si过渡金属化导致形成稳定的氧杂铂环。与Pd（II）/ Si过渡金属

  DOI：

  10.1021/om980157o

文献信息

• Isolation of the Transmetalation Step in the Hiyama Cross-Coupling Reaction of Organosilanes
  作者：Cristina Mateo、Carolina Fernández-Rivas、Antonio M. Echavarren、Diego J. Cárdenas

  DOI：10.1021/om970085l

  日期：1997.5.1

  oxidative addition of o-(Me2RSiCH2O)C6H4I (R = Me, Ph, F) to palladium(0) complexes leads to the corresponding complexes o-(Me2RCH2O)C6H4Pd(L2)I (L = PPh3, AsPh3; L2 = dppf). The intramolecular Pd/Si transmetalation proceeds smoothly with fluorides and carbonates as the promoters.

  将邻-（Me 2 RSiCH 2 O）C 6 H 4 I（R = Me，Ph，F）氧化添加到钯（0）配合物中会生成相应的配合物o-（Me 2 RCH 2 O）C 6 H 4 Pd（L 2）I（L = PPh 3，AsPh 3 ; L 2 = dppf）。分子内的Pd / Si过渡金属化以氟化物和碳酸盐为促进剂顺利进行。
• Mechanistic Significance of the Si–O–Pd Bond in the Palladium-Catalyzed Cross-Coupling Reactions of Alkenylsilanolates
  作者：Steven A. Tymonko、Russell C. Smith、Andrea Ambrosi、Scott E. Denmark

  DOI：10.1021/jacs.5b02515

  日期：2015.5.20

  Through the combination of reaction kinetics (both catalytic and stoichiometric) and solid-state characterization of arylpalladium(II) alkenylsilanolate complexes, the intermediacy of covalent adducts containing Si-O-Pd linkages in the cross-coupling reactions of organosilanolates has been unambiguously established. Two mechanistically distinct pathways have been demonstrated: (1), transmetalation via a neutral 8-Si-4 intermediate that dominates in the cross-coupling of potassium allenylsilanolates, and (2) transmetalation via an anionic 10-Si-5 intermediate that dominates in the cross-coupling of cesium alkenylsilanolates. Arylpalladium(II) alkenylsilanolate complexes bearing various phosphine ligands (both bidentate and monodentate) have been isolated, frilly characterized, and evaluated for their kinetic, competence under thermal (stoichiometric) and anionic (catalytic) conditions. Comparison of the rates for thermal and anionic activation demonstrates that intermediates containing the Si-O-Pd linkage are involved in the cross-coupling process.