trans-iodo(tert-butyldiphenylsilyl benzoate-C3)bis(triphenylphosphine)platinum(II) | 360048-21-1

• 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: trans-iodo(tert-butyldiphenylsilyl benzoate-C3)bis(triphenylphosphine)platinum(II)
• 英文别名: [tert-butyl(diphenyl)silyl] benzoate;platinum(2+);triphenylphosphane;iodide
• CAS: 360048-21-1
• 化学式: C₅₉H₅₃IO₂P₂PtSi
• 分子量: 1206.09
• InChiKey: SBPHZLCZJBATDU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  11.98
• 重原子数：
  66
• 可旋转键数：
  12
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  异烟酸 、 trans-iodo(tert-butyldiphenylsilyl benzoate-C3)bis(triphenylphosphine)platinum(II) 在 CF₃SO₃H 作用下， 以 二氯甲烷 为溶剂， 生成 trans-(benzoic acid-C3)(isonicotinic acid)bis(triphenylphosphine)platinum(II) triflate
  参考文献：
  名称：

  A New Methodology for the Preparation of Cationic Organoplatinum(II) Complexes with Hydrogen-Bonding Functionality

  摘要：

  A new methodology for the preparation, of two series of cationic organoplatinum(II) complexes with hydrogen-bonding functionality is described. The mononuclear complexes of the type trans-[Pt(sigma -aryl)L(PPh3)(2)] OTf (L = nicotinic acid, aryl = C-3-benzoic acid (9) or C-4-benzoic acid (10); L = isonicotinic acid, aryl = C-3-benzoic acid (11) or C-4-benzoic acid (12); OTf = trifluoromethanesulfonate (triflate)) constitute the first series, and the dinuclear complexes of the type trans-[Pt(sigma -aryl)(PPh3)(2)(mu -L)Pt(sigma -aryl)(PPh3)(2)](OTf)(2) (L = 1,1-bis(4-pyridyl)ethene, aryl = C-3-benzoic acid (19) or C-4-benzoic acid (20); L = 4,7-phenanthroline, aryl = C-3-benzoic acid (21) or C-4-benzoic acid (22); L = 4,4 ' -bipyridine, aryl = C-3-benzoic acid (23) or C-4-benzoic acid (24)) constitute the second series. The methodology described here involves the protection of the carboxylic acid group of a 3- or 4-iodobenzoic acid precursor as the tert-butyldiphenylsilyl ester, followed by an oxidative addition reaction of the C-I bond with the Pt(0) species Pt(PPh3)4 to yield the key (sigma -aryl)iodoplatinum(II) intermediates 3 and 4, the structures of which were determined by X-ray crystallography. Subsequent treatment of these products with AgOTf, followed by the addition of a suitable monodentate or bridging bidentate N-donor ligand and, finally, facile removal of the silyl protecting group(s) with HOW affords the target complexes with hydrogen-bonding functionality in high yield. Variable-temperature H-1 NMR experiments with the silyl-protected complexes trans[Pt(sigma -aryl)L(PPh3)(2)]OTf (aryl = C-3-tert-butyldiphenylsilyl benzoate, L = nicotinic acid (5) or isonicotinic acid (7)) confirm that a dynamic intramolecular process involving the pyridyl ligand is occurring. The rotational barrier of a pyridyl ligand in an organoplatinum(II) complex is reported for the first time, where DeltaG(double dagger) = 48.3 +/- 0.9 and 45.7 +/- 0.9 kJ mol(-1) for complexes 5 and 7, respectively.

  DOI：

  10.1021/om010127c
• 作为产物：
  描述：

  四(三苯基膦)铂 、 tert-butyldiphenylsilyl-3-iodobenzoate 以 甲苯 为溶剂， 以98%的产率得到trans-iodo(tert-butyldiphenylsilyl benzoate-C3)bis(triphenylphosphine)platinum(II)
  参考文献：
  名称：

  A New Methodology for the Preparation of Cationic Organoplatinum(II) Complexes with Hydrogen-Bonding Functionality

  摘要：

  A new methodology for the preparation, of two series of cationic organoplatinum(II) complexes with hydrogen-bonding functionality is described. The mononuclear complexes of the type trans-[Pt(sigma -aryl)L(PPh3)(2)] OTf (L = nicotinic acid, aryl = C-3-benzoic acid (9) or C-4-benzoic acid (10); L = isonicotinic acid, aryl = C-3-benzoic acid (11) or C-4-benzoic acid (12); OTf = trifluoromethanesulfonate (triflate)) constitute the first series, and the dinuclear complexes of the type trans-[Pt(sigma -aryl)(PPh3)(2)(mu -L)Pt(sigma -aryl)(PPh3)(2)](OTf)(2) (L = 1,1-bis(4-pyridyl)ethene, aryl = C-3-benzoic acid (19) or C-4-benzoic acid (20); L = 4,7-phenanthroline, aryl = C-3-benzoic acid (21) or C-4-benzoic acid (22); L = 4,4 ' -bipyridine, aryl = C-3-benzoic acid (23) or C-4-benzoic acid (24)) constitute the second series. The methodology described here involves the protection of the carboxylic acid group of a 3- or 4-iodobenzoic acid precursor as the tert-butyldiphenylsilyl ester, followed by an oxidative addition reaction of the C-I bond with the Pt(0) species Pt(PPh3)4 to yield the key (sigma -aryl)iodoplatinum(II) intermediates 3 and 4, the structures of which were determined by X-ray crystallography. Subsequent treatment of these products with AgOTf, followed by the addition of a suitable monodentate or bridging bidentate N-donor ligand and, finally, facile removal of the silyl protecting group(s) with HOW affords the target complexes with hydrogen-bonding functionality in high yield. Variable-temperature H-1 NMR experiments with the silyl-protected complexes trans[Pt(sigma -aryl)L(PPh3)(2)]OTf (aryl = C-3-tert-butyldiphenylsilyl benzoate, L = nicotinic acid (5) or isonicotinic acid (7)) confirm that a dynamic intramolecular process involving the pyridyl ligand is occurring. The rotational barrier of a pyridyl ligand in an organoplatinum(II) complex is reported for the first time, where DeltaG(double dagger) = 48.3 +/- 0.9 and 45.7 +/- 0.9 kJ mol(-1) for complexes 5 and 7, respectively.

  DOI：

  10.1021/om010127c

文献信息

• Synthesis and redistribution reactions of asymmetric σ-arylplatinum(II) complexes containing 4,7-phenanthroline
  作者：David P. Gallasch、Susan L. Woodhouse、Louis M. Rendina

  DOI：10.1016/j.jorganchem.2004.01.027

  日期：2004.4

  The mononuclear σ-aryl complexes of the type trans-[Pt(σ-C6H4R)(4,7-phen)(PPh3)2]OTf (R=4-CO2SitBuPh2, 4-CONHMe, 3-CO2SitBuPh2, 3-CONHMe; OTf=trifluoromethanesulfonate) containing a monodentate 4,7-phenanthroline (4,7-phen) ligand were prepared by an oxidative addition reaction of an aryl iodide with Pt(PPh3)4 to yield the key iodoplatinum(II) precursors trans-[PtI(σ-C6H4R)(PPh3)2], followed by halogen

  该类型的单核σ -芳基配合物的反式- [PT（σ-C 6 H ^ 4 R）（4,7-phen）的（PPH 3）2 ]光学传递函数（R = 4-CO 2的Si吨BUPH 2，4-通过芳基碘化物与Pt（PPh）的氧化加成反应制备含有单齿4,7-菲咯啉（4,7-phen）配体的CONHMe，3-CO 2 Si t BuPh 2，3 -CONHMe; OTf =三氟甲磺酸盐3）4得到关键的碘化铂（II）前体反式-[PtI（σ- C6 H 4 R）（PPh 3）2]，然后进行卤素当量与一当量的4,7-phen置换。的反应反式[PT（σ-C - 6 ħ 4 R）（4,7-phen）的（PPH 3）2 ]光学传递函数与该类型的不稳定配合反式- [PT（OTF）L- 2（σ-C 6 H 4 R '）]]（L = PEt 3，R ' = H; L = PPh 3，R ' = 4-CO 2 Si t BuPh
• A New Methodology for the Preparation of Cationic Organoplatinum(II) Complexes with Hydrogen-Bonding Functionality
  作者：David P. Gallasch、Edward R. T. Tiekink、Louis M. Rendina

  DOI：10.1021/om010127c

  日期：2001.8.1

  A new methodology for the preparation, of two series of cationic organoplatinum(II) complexes with hydrogen-bonding functionality is described. The mononuclear complexes of the type trans-[Pt(sigma -aryl)L(PPh3)(2)] OTf (L = nicotinic acid, aryl = C-3-benzoic acid (9) or C-4-benzoic acid (10); L = isonicotinic acid, aryl = C-3-benzoic acid (11) or C-4-benzoic acid (12); OTf = trifluoromethanesulfonate (triflate)) constitute the first series, and the dinuclear complexes of the type trans-[Pt(sigma -aryl)(PPh3)(2)(mu -L)Pt(sigma -aryl)(PPh3)(2)](OTf)(2) (L = 1,1-bis(4-pyridyl)ethene, aryl = C-3-benzoic acid (19) or C-4-benzoic acid (20); L = 4,7-phenanthroline, aryl = C-3-benzoic acid (21) or C-4-benzoic acid (22); L = 4,4 ' -bipyridine, aryl = C-3-benzoic acid (23) or C-4-benzoic acid (24)) constitute the second series. The methodology described here involves the protection of the carboxylic acid group of a 3- or 4-iodobenzoic acid precursor as the tert-butyldiphenylsilyl ester, followed by an oxidative addition reaction of the C-I bond with the Pt(0) species Pt(PPh3)4 to yield the key (sigma -aryl)iodoplatinum(II) intermediates 3 and 4, the structures of which were determined by X-ray crystallography. Subsequent treatment of these products with AgOTf, followed by the addition of a suitable monodentate or bridging bidentate N-donor ligand and, finally, facile removal of the silyl protecting group(s) with HOW affords the target complexes with hydrogen-bonding functionality in high yield. Variable-temperature H-1 NMR experiments with the silyl-protected complexes trans[Pt(sigma -aryl)L(PPh3)(2)]OTf (aryl = C-3-tert-butyldiphenylsilyl benzoate, L = nicotinic acid (5) or isonicotinic acid (7)) confirm that a dynamic intramolecular process involving the pyridyl ligand is occurring. The rotational barrier of a pyridyl ligand in an organoplatinum(II) complex is reported for the first time, where DeltaG(double dagger) = 48.3 +/- 0.9 and 45.7 +/- 0.9 kJ mol(-1) for complexes 5 and 7, respectively.