[(bis(dicyclohexylphosphino)ethane)Pt(H)(CH2-t-Bu)] | 158238-87-0

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: [(bis(dicyclohexylphosphino)ethane)Pt(H)(CH2-t-Bu)]
• 英文别名: [(dcpe)Pt(H)(CH2-t-Bu)]
• CAS: 158238-87-0
• 化学式: C₃₂H₆₂P₂Pt
• 分子量: 703.872
• InChiKey: HKQLVCGVTJAFGQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(bis(dicyclohexylphosphino)ethane)Pt(H)(CH2-t-Bu)] 以 环己烷 为溶剂， 生成
  参考文献：
  名称：

  C-H Activation by [Bis(dialkoxyphosphino)ethane]platinum(0) and [Bis(diaminophosphino)ethane]platinum(0) Complexes: Platinum-Platinum Dimer Formation Limits Yields

  摘要：

  Syntheses, of new bidentate phosphorus-containing ligands and platinacycles that insert into C-H bonds of unactivated hydrocarbons under mild conditions are reported. The reactivities of the platinum neopentyl hydride species can be substantially increased by introducing oxygen- or nitrogen-containing substituents onto the phosphorus atoms. Dimeric species that are formed from the Pt(0) species are identified by comparing their P-31 NMR spectra with simulated spectra. Further evidence for these dimers was obtained by cleaving them to mononuclear derivatives with alkyne and phosphine ligands. Formation of these dimers limits the efficiency of hydrocarbon activation. The extent of dimerization that occurs during alkane activation depends upon the steric crowdedness about the Pt(0) center. The X-ray structure of [-(CH2)4-C(CH2O)2]PCH2CH2P[(OCH2)2C-(CH2)4-]Pt(neo-Pe)Cl (9) has been determined: C21H39O4PtCl2.CH2Cl2, M(r) = 732.96, monoclinic, space group P2(1)/n (No. 14), a = 14.667(3) angstrom b = 11.384(6) angstrom, c = 17.110(4) angstrom, beta = 100.62(2)-degrees, V= 2808(3) angstrom3, z = 4, D(calc) = 1.734 g CM-3, mu(Mo Kalpha) = 54.74 cm-1, R = 0.048, R(w) = 0.055.

  DOI：

  10.1021/om00020a012
• 作为产物：
  描述：

  在 Na[HB(OCH₃)3] 作用下， 以 四氢呋喃 为溶剂， 生成 [(bis(dicyclohexylphosphino)ethane)Pt(H)(CH2-t-Bu)]
  参考文献：
  名称：

  C-H Activation by [Bis(dialkoxyphosphino)ethane]platinum(0) and [Bis(diaminophosphino)ethane]platinum(0) Complexes: Platinum-Platinum Dimer Formation Limits Yields

  摘要：

  Syntheses, of new bidentate phosphorus-containing ligands and platinacycles that insert into C-H bonds of unactivated hydrocarbons under mild conditions are reported. The reactivities of the platinum neopentyl hydride species can be substantially increased by introducing oxygen- or nitrogen-containing substituents onto the phosphorus atoms. Dimeric species that are formed from the Pt(0) species are identified by comparing their P-31 NMR spectra with simulated spectra. Further evidence for these dimers was obtained by cleaving them to mononuclear derivatives with alkyne and phosphine ligands. Formation of these dimers limits the efficiency of hydrocarbon activation. The extent of dimerization that occurs during alkane activation depends upon the steric crowdedness about the Pt(0) center. The X-ray structure of [-(CH2)4-C(CH2O)2]PCH2CH2P[(OCH2)2C-(CH2)4-]Pt(neo-Pe)Cl (9) has been determined: C21H39O4PtCl2.CH2Cl2, M(r) = 732.96, monoclinic, space group P2(1)/n (No. 14), a = 14.667(3) angstrom b = 11.384(6) angstrom, c = 17.110(4) angstrom, beta = 100.62(2)-degrees, V= 2808(3) angstrom3, z = 4, D(calc) = 1.734 g CM-3, mu(Mo Kalpha) = 54.74 cm-1, R = 0.048, R(w) = 0.055.

  DOI：

  10.1021/om00020a012

文献信息

• The reaction of the group-13 alkyls ER3 (E=Al, Ga, In; R=CH2t-Bu, CH2 SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)]
  作者：Roland A. Fischer、Dana Weiß、Manuela Winter、Iris Müller、Herbert D. Kaesz、Nikolaus Fröhlich、Gernot Frenking

  DOI：10.1016/j.jorganchem.2004.09.059

  日期：2004.11

  The reactions of the sterically demanding group-13 alkyls ER3 (E = Al, Ga, In; R = CH2t-Bu, CH2SiMe3) with the platinum-complex [(dcpe)Pt(H)(CH2t-Bu)] were re-investigated. The bimetallic compounds [(dcpe)Pt(ER2)(R)] (3: E = Ga, R = CH2SiMe3; 5: E = In, R = CH2t-Bu; dcpe = bis(dicyclohexylphosphino)ethane) with direct σ(Pt–E) bonds were obtained by oxidative addition of an E-C bond to the coordinatively

  具有空间需求的13位烷基ER 3（E = Al，Ga，In; R = CH 2 t -Bu，CH 2 SiMe 3）与铂络合物[（dCPE）Pt（H）（CH 2 t -Bu）]被重新调查。双金属化合物[（dCPE）Pt（ER 2）（R）]（3：E = Ga，R = CH 2 SiMe 3 ; 5：E = In，R = CH 2 t -Bu; dCPE =双（二环己基膦基）通过将EC键氧化加成到原位生成的配位不饱和片段[（dCPE）Pt]中，获得具有直接σ（Pt-E）键的乙烷）通过热分解起始配合物[（dCPE）Pt（CH 2 t -Bu ）（H）]。单晶结构测定表明，Pt-Ga键长为2.376（2）Å，Pt-In键长为2.608（1）Å。所有新化合物均通过元素分析，31 P和195 Pt NMR光谱进行了表征。有趣的是，铂-镓化合物3慢慢转变成铂烷基/氢化异构体（DCPE）的Pt（μ 2 -H）[CH