[Pt(ortho-(di-ortho-tolylphosphino)benzyl)Cl(PPh3)] | 211575-95-0

• 英文名称: [Pt(ortho-(di-ortho-tolylphosphino)benzyl)Cl(PPh3)]
• 英文别名: [PtCl(PPh3)(CH2C6H4-o-P(o-tolyl)2)]
• CAS: 211575-95-0
• 化学式: C₃₉H₃₅ClP₂Pt
• 分子量: 796.187
• InChiKey: RNNKMFNWSIFYAC-UHFFFAOYSA-M

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

• 作为反应物：
  描述：

  [Pt(ortho-(di-ortho-tolylphosphino)benzyl)Cl(PPh3)] 以 甲苯 为溶剂， 以86%的产率得到trans-[Pt(ortho-(di-ortho-tolylphosphino)benzyl)Cl(PPh₃)]
  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
• 作为产物：
  描述：

  [(Pt(CH2C6H4P(o-tolyl)2-κC,P)(μ-Cl))2] 、 三苯基膦 以 二氯甲烷 为溶剂， 生成 [Pt(ortho-(di-ortho-tolylphosphino)benzyl)Cl(PPh3)]
  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

文献信息

• Stabilized Bis-ylides as a Source of Carbene Ligands in Palladium(II) and Platinum(II) Complexes
  作者：Larry R. Falvello、Rosa Llusar、Marina E. Margalejo、Rafael Navarro、Esteban P. Urriolabeitia

  DOI：10.1021/om020467d

  日期：2003.3.1

  2Me)}(L)(PPh3)](ClO4) (L = SC4H8, 9; PPh3, 10), probably through the initial formation of an ylide-carbene complexsimilar to 1−6followed by the migratory insertion of the carbene ligand into the Pd−C(C6F5) bond and coordination of the newly generated ylide function. The crystal structure of complex 1a·CH2Cl2 has been analyzed by X-ray diffraction.

  α稳定的双内酯[Ph 3 P C（CO 2 Me）-C（CO 2 Me）PPh 3 ]与M（II）双溶剂化物衍生物顺式[[M（C 6 F 5）] 2（OC 4 H 8）2 ]或[M（C∧X）（OC 4 H 8）2 ] ClO 4（M = Pd，PT;C∧X=正金属配体），生成ylide-carbene配合物顺式- [M（C 6 F 5）2 C（CO 2 Me）−C（CO 2 Me）（PPh3）}（PPh 3）]（M = PT 1a，Pd 1b）或[M（C∧X）C（CO 2 Me）-C（CO 2 Me）（PPh 3）}（PPh 3）] ClO 4（M = PT，C∧X= ö -CH 2 C ^ 6 ħ 4 P（ø甲苯基）2，2 ; M =钯，C∧X= ö -CH 2 C ^ 6 ħ 4 P（ø甲苯基）2，3 ; CH 2 C ^ 9 ħ 6 N-C 8，N，4 ; NC 5 H ^ 4 -