(dppe)Pt(S-BINOL) | 210770-50-6

• 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: (dppe)Pt(S-BINOL)
• 英文别名: [(1,2-bis(diphenylphosphino)ethane)Pt(S-BINOL)]；2-diphenylphosphanylethyl(diphenyl)phosphane;1-(2-oxidonaphthalen-1-yl)naphthalen-2-olate;platinum(2+)
• CAS: 210770-50-6；429658-13-9
• 化学式: C₄₆H₃₆O₂P₂Pt
• 分子量: 877.818
• InChiKey: PQGYJTCXIYZBEL-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (dppe)Pt(S-BINOL) 、 三氟甲磺酸 以 氯苯 为溶剂， 生成 [Pt(1,2-bis(diphenylphosphino)ethane)(OTf)2]
  参考文献：
  名称：

  与P 2 Pt（OTf）2催化的Diels-Alder反应有关的路易斯酸-路易斯碱配合物之间的热力学和动力学关系

  摘要：

  Pt（II）路易斯酸P 2 Pt（OTf）2（2 ; P 2 = dppe（a），R -BINAP（b）），其催化丙烯酰基-N-恶唑烷酮（4）的Diels-Alder反应通过用2当量的三氟甲磺酸（HOTf）活化P 2 Pt（S -BINOL）前体1原位生成环戊二烯（HCp ）。催化剂2和催化相关的路易斯酸-路易斯碱配合物[P 2的Pt（L 2）] 2+ [光学传递函数] - 2（L 2用1 H和195 K的31 P NMR光谱表征= 2 H 2 O（3），亲二烯体4（6），Diels-Alder加合物5（8）。2a也用X射线晶体学表征。之间的热力学关系2，3，6，8，和一个BF 4 -的类似物2是通过竞争性结合实验中测定监测由31在195 K的1 H NMR，以评估抗衡离子，添加剂和产物的竞争性抑制对底物与催化剂的配位作用。这些实验表明，路易斯碱结合[P 2的Pt] 2+与相对强度BF 4

  DOI：

  10.1021/om0109861

文献信息

• (dppe)Pt(OTf)₂ and (<i>R</i>-BINAP)Pt(OTf)₂ Lewis Acids Catalyze the Diels−Alder Reaction by Different Mechanisms
  作者：Nicole M. Brunkan、Michel R. Gagné

  DOI：10.1021/om010987t

  日期：2002.4.1

  include a broad singlet at 12.7 ppm, are also formed. Both catalyst decomposition and Diels−Alder catalysis proceeded faster in reactions involving dppe Lewis acid 2a than in those involving R-BINAP Lewis acid 2b. In the 2b reaction at 195 K, Pt-bound dienophile 4 was immediately converted to the Pt-bound Diels−Alder adduct 2S-5 on addition of HCp; however, no turnover occurred and no η5-Cp complex was

  原位观察，通过195-240 K的31 P和1 H NMR，由Pt（II）路易斯酸P 2 Pt（OTf）催化的丙烯酰基-N-恶唑烷酮（4）/环戊二烯（HCP）Diels-Alder反应2（2，P 2 = DPPE（一），- [R -BINAP（b））显示，该ditriflate催化剂通过HCP以不同的速率消耗，以产生催化失活的18-电子络合物[P 2的Pt（η 5 -CP） ] + [OTf] -（9）。机制研究指向从所提出的中间二烯HOTf的正式损失复杂[P 2的Pt（HCP）] 2+ [光学传递函数] - 2，通过HCP的必要第二等效提供便利; 还形成了不明确的HCP / HOTf副产物，其1 H NMR共振包括12.7 ppm的宽单峰。在涉及DPPE路易斯酸2a的反应中，催化剂的分解和Diels-Alder催化均比在涉及R- BINAP路易斯酸2b的反应中进行得更快。在195 K的2
• NMR Structure of an Unusual Pt₂(μ-BINOL) Dimer:  More Surprises from a Seemingly Simple Chiral Ligand
  作者：Nicole M. Brunkan、Michel R. Gagné

  DOI：10.1021/om0204888

  日期：2002.10.1

  A novel [(dppe)(2)Pt-2(mu-BINOL)](2+)[OTf](-)(2) dimer (A) was cleanly produced by addition of 1 equiv of HOTf to (dppe)Pt(S-BINOL) (1) or via "comproportionation" of I with (dppe)Pt-(OTf)(2) (2). The structure of A was investigated by H-1, P-31, and C-13 NMR spectroscopy, as well as 2D H-1/H-1 (COSY) and C-13/H-1 (HMQC, HMBC) correlation experiments, revealing that both halves of the bridging BINOL ligand have undergone "enol-keto" tautomerization in this complex. Two symmetry-equivalent (dppe)Pt fragments coordinate in an anti fashion via Pt-C sigma bonds to the adjacent atoms C-1 and C-1' of the resulting "diketo" BINOL ligand. eta(1)-Coordination of the carbonyl groups of "diketo" BINOL to Pt was proposed to fill the fourth coordination site of each Pt square plane in dimer A, generating favorable five-membered Pt-chelate rings; the P-Pt coupling constants observed for A are consistent with C=O-->Pt coordination. The driving force for dimer formation is likely electrostatic, as dimerization distributes the dicationic charge of Pt Lewis acid 2 over two Pt centers, facilitated by the "diketo" BINOL bridge.