trans-(benzoic acid-C3)(nicotinic acid)bis(triphenylphosphine)platinum(II) triflate | 360048-32-4

• 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-(benzoic acid-C3)(nicotinic acid)bis(triphenylphosphine)platinum(II) triflate
• 英文别名: benzoic acid;platinum(2+);pyridine-3-carboxylic acid;trifluoromethanesulfonate;triphenylphosphane
• CAS: 360048-32-4
• 化学式: CF₃O₃S*C₄₉H₄₀NO₄P₂Pt
• 分子量: 1112.96
• InChiKey: CEXCOPCOHDYVPQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  8.9
• 重原子数：
  65
• 可旋转键数：
  8
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.02
• 拓扑面积：
  153
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  trans-(nicotinic acid)(tert-butyldiphenylsilyl benzoate-C3)bis(triphenylphosphine)platinum(II) triflate 在 CF₃SO₃H 作用下， 以 二氯甲烷 为溶剂， 以75%的产率得到trans-(benzoic acid-C3)(nicotinic 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

文献信息

• 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.