[Pt(ortho-(di-ortho-tolylphosphino)benzyl)(NCCH=PPh3)(PPh3)]ClO4 | 211576-03-3

• 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: [Pt(ortho-(di-ortho-tolylphosphino)benzyl)(NCCH=PPh3)(PPh3)]ClO4
• CAS: 211576-03-3
• 化学式: C₅₉H₅₁NP₃Pt*ClO₄
• 分子量: 1161.51
• InChiKey: PBARGUMZODLBFT-UHFFFAOYSA-M

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

• 作为产物：
  描述：

  [Pt(ortho-(di-ortho-tolylphosphino)benzyl)(NCMe)(PPh3)]ClO4 、 (三苯基膦)乙腈 以 二氯甲烷 为溶剂， 以44%的产率得到[Pt(ortho-(di-ortho-tolylphosphino)benzyl)(NCCH=PPh3)(PPh3)]ClO4
  参考文献：
  名称：

  Synthesis, structure and reactivity of PtII complexes containing the [o-(di-o-tolylphosphino)benzyl] cyclometalated ligand towards α-stabilized phosphorus ylides

  摘要：

  The reaction of [Pt(C <^> P)(NCMe)(2)]ClO4 2 [C <^> P = ortho -(di-ortho-tolylphosphino)benzyl], with the alpha-stabilized phosphorus ylides Ph3P=C(H)R (R=COMe, COPh, COOMe, CN) in a 1:1 molar ratio results in the formation of [Pt(C <^> P){C(H)(R)PPh3}(NCMe)]ClO4 (R = COMe 3, COPh 4, COOMe 5. CN 6). Complexes 3-6 appear as single isomers in which the ylide is selectively C-coordinated trans to the P atom of the C <^> P ligand. The displacement of the remaining coordinated NCMe ligand by adding more ylide was only successfully accomplished with Ph3P=C(H)CN, giving [Pt(C<^>P){C(H)(CN)PPh3} (NC-C(H)PPh3)]ClO4 7, in which one ylide is C-coordinated trans to the P atom of the C <^> P ring and the other ylide is N-coordinated trans to the C atom, showing the ambidentate character of Ph3P=C(H)CN as a ligand. The reaction of [Pt(C <^> P)(mu-Cl)](2) 1 with PPh3 (1:2 molar ratio, CH2Cl2, r.t.) results in the formation of the two expected isomers trans- and cis-[Pt(C<^> P)Cl(PPh3)] (8 and 9, respectively). The trans isomer 8 is obtained as a single product by heating the mixture of isomers in toluene or, in one step, by carrying out the reaction of I with PPh3 in refluxing toluene. Treatment of 8 with TICIO4 in NCMe gives trans-[Pt(C <^> P)(PPh3)(NCMe)]ClO4 10 which can also be obtained by the reaction of 2 with PPh3. Complex 10 reacts with Ph3P=C(H)R (R = COMe, COOMe, CN) in a 1:1 molar ratio resulting in the displacement of the NCMe ligand and the formation of [Pt(C <^> P)Cl{C(H)(R')= C(H)PPh3}PPh3]ClO4 (R' = Me 11, OMe 12) or [Pt(C <^> P) {NC-C(H)=PPh3}PPh3]ClO4 13 in which the ylide ligand is selectively O- (11, 12) or N-coordinated (13). The reaction of [Pt(C<^> P)(mu-Cl)](2) 1 with Ph3P=C(H)R (R = COMe, COOMe, CN) in a 1:2 molar ratio results in the cleavage of the chlorine-bridge system and the formation of [Pt(C <^> P)Cl{C(H)(R)PPh3}] (R = COMe 14, COOMe 15, CN 16) as single isomers in which the ylide is C-coordinated ti ans to the P atom of the C<^>P ligand. Complex 14 reacts with TICIO4 and Ph3P=C(H)COMe (1:1:1 molar ratio) giving [Pt(C <^> P){OC(Me)=C(H)PPh3}(2)]ClO4 17. Complex 17 shows two interesting features: the isomerization of the C-linked ylide in 14 to an O-bonded one in 17 and the simultaneous presence of two O-coordinated ylides to the same metal center. The selectivity in the observed coordination modes and the preferred coordination of the ylides trans to the P atom of the C<^>P ligand are discussed in terms of electronic and steric factors. (C) 1998 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(98)00550-6