[Pt(2,6-bis(diphenylphosphinomethyl))CH₂CHO]BF₄ | 1350342-71-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Pt(2,6-bis(diphenylphosphinomethyl))CH₂CHO]BF₄
• 英文别名: [Pt(PNP)CH₂CHO]BF₄；[Pt(2,6-bis(diphenylphosphinomethyl)pyridine)CH2CHO]BF4；acetaldehyde;[6-(diphenylphosphanylmethyl)pyridin-2-yl]methyl-diphenylphosphane;platinum(2+);tetrafluoroborate
• CAS: 1350342-71-0
• 化学式: BF₄*C₃₃H₃₀NOP₂Pt
• 分子量: 800.439
• InChiKey: BFSKEUNRBPMUDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.66
• 重原子数：
  43
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  30
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  盐酸 、 [Pt(2,6-bis(diphenylphosphinomethyl))CH₂CHO]BF₄ 以 二氯甲烷-D2 为溶剂， 生成 [Pt(2,6-bis(diphenylphosphinomethyl)pyridine)(Cl)](1+)
  参考文献：
  名称：

  Water Addition to Alkynes Promoted by a Dicationic Platinum(II) Complex

  摘要：

  Dicationic platinum alkyne complexes were generated in situ by substitution of ethylene in [Pt(PNP)(C2H4)]-(BF4)(2) (PNP = 2,6-bis(diphenylphosphinomethyl)pyridine) with alkynes at low temperature. The dicationic acetylene complex readily adds water to form the platina-acetaldehyde complex [Pt(PNP)(CH2CHO)BF4, which was analyzed by X-ray diffraction. H-1 and P-31 NMR. studies were performed to elucidate the mechanism of formation of [Pt(PNP)(CH2CHO)BF4. A reversible acid base equilibrium between the platina-acetaldehyde and the corresponding eta(2)-vinyl alcohol complex [Pt(PNP)(CH2= CHOH)](2+) was observed. The complexes with terminal alkynes (propyne and 1-hexyne) gave with water a mixture of Markovnikov and anti-Markovnikov addition products [Pt(PNP){CH2C(O)R-1}BF4 and [Pt(PNP){C(O)CH2R1}]BF4 (R-1 = Me, n-Bu) in a ratio of 1:4. However, with tert-butyl- and phenylacetylene C H bond activation occurred, yielding the sigma-alkynyl complexes [Pt(PNP)(C equivalent to CR2)BF4 (R-2 = t-Bu, Ph). Complexes with internal allcynes (RC)-C-3 equivalent to CR4 (R-3 = Me; R-4 = Me, n-Pr) react with water and form the corresponding beta-ketonyl complexes [Pt(PNP){(CHRC)-C-3(O)R-4}]BF4. Moderate regioselectivity was observed for 2-hexyne.

  DOI：

  10.1021/om2007908
• 作为产物：
  描述：

  [Pt(2,6-bis(diphenylphosphinomethyl)pyridine)(C₂H₄)](BF₄)₂ 、 水 、 乙炔 以 二氯甲烷 为溶剂， 以82%的产率得到[Pt(2,6-bis(diphenylphosphinomethyl))CH₂CHO]BF₄
  参考文献：
  名称：

  Water Addition to Alkynes Promoted by a Dicationic Platinum(II) Complex

  摘要：

  Dicationic platinum alkyne complexes were generated in situ by substitution of ethylene in [Pt(PNP)(C2H4)]-(BF4)(2) (PNP = 2,6-bis(diphenylphosphinomethyl)pyridine) with alkynes at low temperature. The dicationic acetylene complex readily adds water to form the platina-acetaldehyde complex [Pt(PNP)(CH2CHO)BF4, which was analyzed by X-ray diffraction. H-1 and P-31 NMR. studies were performed to elucidate the mechanism of formation of [Pt(PNP)(CH2CHO)BF4. A reversible acid base equilibrium between the platina-acetaldehyde and the corresponding eta(2)-vinyl alcohol complex [Pt(PNP)(CH2= CHOH)](2+) was observed. The complexes with terminal alkynes (propyne and 1-hexyne) gave with water a mixture of Markovnikov and anti-Markovnikov addition products [Pt(PNP){CH2C(O)R-1}BF4 and [Pt(PNP){C(O)CH2R1}]BF4 (R-1 = Me, n-Bu) in a ratio of 1:4. However, with tert-butyl- and phenylacetylene C H bond activation occurred, yielding the sigma-alkynyl complexes [Pt(PNP)(C equivalent to CR2)BF4 (R-2 = t-Bu, Ph). Complexes with internal allcynes (RC)-C-3 equivalent to CR4 (R-3 = Me; R-4 = Me, n-Pr) react with water and form the corresponding beta-ketonyl complexes [Pt(PNP){(CHRC)-C-3(O)R-4}]BF4. Moderate regioselectivity was observed for 2-hexyne.

  DOI：

  10.1021/om2007908

文献信息

• Mechanistic Studies on Platinum(II) Catalyzed Hydroarylation of Alkynes
  作者：Christine Hahn、Mayra Miranda、Nagendra P. B. Chittineni、Trent A. Pinion、Ricardo Perez

  DOI：10.1021/om5003123

  日期：2014.6.23

  The dicationic acetylene platinum(II) complex [Pt(PNP)(C2H2)](BF4)(2) (PNP = 2,6-bis(diphenylphosphinomethyl)pyridine) was generated in situ by ligand substitution from the ethylene complex [Pt(PNP)(C2H4)](BF4)(2) and was reacted with a series of arenes at low temperature. Only electron-rich arenes added across the coordinated C-C triple bond and gave the corresponding arylalkenyl complexes (E)-[Pt(PNP)(CH=CHAr)]BF4 (Ar = C6Me5, C6H2Me3-2,4,6, C6H3Me2-2,6, C6H3Me2-2,4). A slow E-Z isomerization of the arylalkenyl complexes was observed. Single-crystal X-ray structure analyses were obtained for both E and Z isomers of the pentamethylbenzene derivative. The E isomers of [Pt(PNP)(CH=CHAr)]BF4 (Ar = C6Me5, C6H2Me3-2,4,6) reacted with excess HBF4 center dot Et2O to give the corresponding arylalkene complexes [Pt(PNP)(CH2=CHAr)](BF4)(2), whereas the Z isomers did not undergo immediate protonolysis. Using (E)-[Pt(PNP)(CD=CDC6Me5)]BF4 it was shown that the stereochemistry of the C-C double bond in the protonolysis product depends on the nature of the acid anion HX (X- = Cl-, BF4-). The catalytic hydroarylation was studied in solution by NMR spectroscopy. The reaction studies provide a more refined view of the individual steps proposed for the Friedel-Crafts type mechanism of the Pt-II-catalyzed intermolecular hydroarylation of alkynes.