Pt(1,2-bis(diphenylphosphino)ethane)diphenylacetylene | 69101-79-7

• 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: Pt(1,2-bis(diphenylphosphino)ethane)diphenylacetylene
• 英文别名: (bis(diphenylphosphino)ethane)Pt(PhCCPh)；2-Diphenylphosphanylethyl(diphenyl)phosphane;2-phenylethynylbenzene;platinum
• CAS: 69101-79-7
• 化学式: C₄₀H₃₄P₂Pt
• 分子量: 771.737
• InChiKey: RBSKDFXBOQADGR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.34
• 重原子数：
  43
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  Pt(1,2-bis(diphenylphosphino)ethane)diphenylacetylene 以 氘代苯 为溶剂， 以45%的产率得到(dppe)PtPh(CCPh)
  参考文献：
  名称：

  带有螯合P，N-和P，P-配体的Pt（0）-二苯乙炔配合物中的碳-碳键活化。

  摘要：

  DOI：

  10.1021/ja016675z
• 作为产物：
  描述：

  [platinum(II)dichloride(1,2-bis(diphenylphosphino)ethane)] 、 二苯基乙炔 以 乙腈 、 苯 为溶剂， 生成 Pt(1,2-bis(diphenylphosphino)ethane)diphenylacetylene
  参考文献：
  名称：

  CX and CH cleavage by electrochemically generated non-linear [PtL2] complexes

  摘要：

  The electrochemical reduction of [PtX2L2] (X = halide, L2 = bidentate diphosphine: Ph2PCH2CH2PPh2, dppe; Cy2PCH2CH2PCy2, dcpe; Cy2P{CH2}3PCy2, dcpp) has been used as a method of generating non-linear [PtL2] compounds whose reactivity with substrates Ar-X (X = Cl, Br, CN, H, C=CPh) has been examined. Generation of [PtL2] (L2 = dppe or dcpe) in the presence of excess Ph - X (X = Cl, Br) produces [PtXPhL2] efficiently. Similarly, generation of [PtL2] (L2 = dppe or dcpe) in the presence of PhC=CPh results in trapping to form [PtL2(PhC=CPh)]. Generation of [PtL2] (L2 = dppe or dcpe) in the presence of PhCN or PhH results in indiscriminate reactions that do not produce tractable products. In contrast, reduction of [PtCl2(dcpp)] in CH3CN/C6H6/Bu4NClO4 produces [PtHPh(dcpp)] with considerable selectivity via aromatic C-H activation by [Pt(dcpp)]. At room temperature the complex [PtHPh(dcpp)] undergoes exchange with C6D6 to generate [PtD(C6D5)(dcpp)].

  DOI：

  10.1016/s0277-5387(00)86908-9

文献信息

• Photochemical reactions of diphosphineplatinum(II) oxalate complexes
  作者：Gordon K. Anderson、Gregg J. Lumetta、Jeffrey W. Siria

  DOI：10.1016/0022-328x(92)83310-e

  日期：1992.8

  cations. Simple elimination of CO2 does not occur in all cases, as illustrated by the formation of [pt(CO2Me)2(dppe)] when [Pt(C2O4)(dppe)] is photolyzed in the presence of methanol. Photochemical reactions of the related complexes [Pt(C2O4)L2] (L2  dppm, dcpe) are also described.

  在[Pt（C 2 O 4）（dppe）]的CH 3 CN / C 6 H 6或PhCN溶液中于254 nm照射产生2当量。的CO 2，并在PhCl或PhI的存在下产生[PtX 2（dppe）]（X = Cl，I）。使用CO或PhCCPh时，产物为[Pt（CO）2（dppe）]或[Pt（PhCPh）（dppe）]，但在后者的情况下，延长的光解产率为[PtPh（CCPh）（dppe） ]。在H 2存在下进行光解得到[Pt 2 H 3（dppe）2 ] +和[Pt 3 H 3（dppe）3 ] +的混合物阳离子。如在甲醇存在下光解[Pt（C 2 O 4）（dppe）]时形成[pt（CO 2 Me）2（dppe）] ，这说明在所有情况下都不会简单地消除CO 2。 。还描述了相关配合物[Pt（C 2 O 4）L 2 ]（L 2 dppm，dcpe）的光化学反应。
• Synthesis and structures of platinum diphenylacetylene and dithiolate complexes bearing diphosphinidenecyclobutene ligands (DPCB-Y)
  作者：Yumiko Nakajima、Mitsuharu Nakatani、Kyohei Hayashi、Yu Shiraishi、Ryo Takita、Masaaki Okazaki、Fumiyuki Ozawa

  DOI：10.1039/c0nj00118j

  日期：——

  A series of platinum complexes of the type [Pt(D)(A)] having two kinds of π-conjugated ligand systems with donor and acceptor properties are prepared, using p-substituted diphenylacetylenes (tolan-X; X = OMe, H, CF3), 1,2-benzenedithiolato (bdt) and 1,3-dithia-2-thione-4,5-dithiolato (dmit) as π-donor ligands (D), and 1,2-diaryl-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutenes (DPCB-Y; diaryl = 2C6H4-p-Y (Y = OMe, H, CF3), biphenyl-2,2′-diyl) as π-acceptor ligands (A). The electronic structures of the resulting complexes are examined in detail to investigate π-orbital interaction occurring in DPCB-Y complexes with a low-coordinate phosphorus ligand. The 31P NMR chemical shifts are highly sensitive to the Pt–P distances of the complexes, and linearly correlated with the bond lengths. The UV-vis absorption spectra of [Pt(tolan-X)(DPCB-Y)] display π–π* transitions in the visible region, which are shifted to longer wavelengths as the electron-donating ability of X and electron-withdrawing ability of Y increase, respectively. The complex [Pt(tolan-OMe)(DPCB-CF3)] with a donor–acceptor combination of substituents exhibits particularly low-energy absorption. The absorption is further red-shifted for [Pt(bdt)(DPCB-phen)] and [Pt(dmit)(DPCB-phen)] having dithiolates as strong π-donor ligands.

  一系列类型为[Pt(D)(A)]的铂配合物被合成，具有两种具有给体和受体性质的π共轭配体系统，使用p取代的二苯乙炔（tolan-X；X = OMe、H、CF3）、1,2-苯并二硫醇盐（bdt）和1,3-二硫-2-硫酮-4,5-二硫醇盐（dmit）作为π给体配体（D），以及1,2-二芳基-3,4-双[(2,4,6-三叔丁基苯)膦烯]环丁烯（DPCB-Y；二芳基 = 2C6H4-p-Y（Y = OMe、H、CF3），联苯-2,2′-二基）作为π受体配体（A）。对所得配合物的电子结构进行了详细研究，以探讨在低配位磷配体的DPCB-Y配合物中发生的π轨道相互作用。31P NMR化学位移对配合物的Pt–P距离高度敏感，并与键长呈线性相关。配合物[Pt(tolan-X)(DPCB-Y)]的紫外-可见吸收光谱在可见区域显示π–π*跃迁，随着X的给电子能力和Y的吸电子能力的提高而向更长波长移动。具有给体-受体取代基组合的配合物[Pt(tolan-OMe)(DPCB-CF3)]显示出特别低的能量吸收。对于具有二硫醇盐作为强π给体配体的[Pt(bdt)(DPCB-phen)]和[Pt(dmit)(DPCB-phen)]，吸收进一步红移。
• Synthesis of heterodinuclear hydride complexes by oxidative addition of a transition-metal hydride to Pt(0) and Pd(0) complexes
  作者：Nobuyuki Komine、Ayako Kuramoto、Toshiyuki Yasuda、Tatsuya Kawabata、Masafumi Hirano、Sanshiro Komiya

  DOI：10.1016/j.jorganchem.2015.04.048

  日期：2015.9

  reductive elimination at the Pt or Pd center to give the Pt(alkene or alkyne)(dppe) and MHLn,, suggesting reversibility of this process. The DFT calculations suggest that these reactions are controlled by the thermodynamic stability and the electron rich alkene complex of Pt(0) (or Pd(0)) are preferable to prepare these heterodinuclear hydride complexes by the oxidative addition.

  异 核氢化铂和-钯配合物，（dppe）HPt-ML n（ML n = MoCp（CO）3（3a），WCp（CO）3（3b）），（dppe）Pt（μ-H）（μ-CO ）Mn（CO）4（3c），（dppe）Pt（μ-H）（μ-CO）FeCp（CO）（3d），顺式L.′2个HPT - ML Ñ（5AA：L'= PPH 3 ; ML Ñ  = MOCP（CO）3，5BA：L'= PPH 3 ; ML Ñ  = WCP（CO）3，5AB：L'= PMePh 2 ; ML Ñ  = MOCP（CO ）3，5AC：L'= PME 2 Ph值; ML ñ  = MOCP（CO）3），（DPPE）的Pd（μ-H）（μ-CO）ML ñ（ML ñ  = MOCP（CO）2（图7a）， WCp（CO）2（7b）），（dppe）Pd（μ-H）（μ-CO）Mn（CO）4（7c）通过将单核过渡金属氢化物络合物氧化加成至
• Synthesis of hydridoplatinum–molybdenum (or tungsten) heterodinuclear complexes by β-hydrogen elimination of (dppe)EtPt–MCp(CO)3. Selective hydride transfer from Pt to Mo (or W)
  作者：Sanshiro Komiya、Toshiyuki Yasuda、Atsushi Fukuoka、Masafumi Hirano

  DOI：10.1016/s1381-1169(00)00171-0

  日期：2000.9

  Hydridoplatinum–molybdenum (or tungsten) heterodinuclear complexes (dppe)HPt–MCp(CO)3 [M=Mo (1), W (2); dppe=1,2-bis(diphenylphosphino)ethane] have been prepared by selective β-hydrogen elimination of corresponding ethylplatinum–molybdenum (or tungsten) complexes (dppe)EtPt–MCp(CO)3 [M=Mo (3), W (4)]. The β-hydrogen elimination process is significantly facilitated by electron-withdrawing transition

  氢铂-钼（或钨）异双核配合物（dppe）HPt-MCp（CO）3 [M = Mo（1），W（2）; 通过选择性β-氢消除相应的乙基铂-钼（或钨）配合物（dppe）EtPt-MCp（CO）3 [M = Mo（3），W （4）]。铂的吸电子过渡金属配体（例如Co（CO）4（5））显着促进了β-氢的消除过程。具有吸电子基团的炔诱导选择性氢化转移反应在这些heterodunucelar复杂1 - 2 得到氢钼（或钨）和零价（乙炔）铂络合物。
• CX and CH cleavage by electrochemically generated non-linear [PtL2] complexes
  作者：Julian A. Davies、Richard J. Staples

  DOI：10.1016/s0277-5387(00)86908-9

  日期：1991.1

  The electrochemical reduction of [PtX2L2] (X = halide, L2 = bidentate diphosphine: Ph2PCH2CH2PPh2, dppe; Cy2PCH2CH2PCy2, dcpe; Cy2PCH2}3PCy2, dcpp) has been used as a method of generating non-linear [PtL2] compounds whose reactivity with substrates Ar-X (X = Cl, Br, CN, H, C=CPh) has been examined. Generation of [PtL2] (L2 = dppe or dcpe) in the presence of excess Ph - X (X = Cl, Br) produces [PtXPhL2] efficiently. Similarly, generation of [PtL2] (L2 = dppe or dcpe) in the presence of PhC=CPh results in trapping to form [PtL2(PhC=CPh)]. Generation of [PtL2] (L2 = dppe or dcpe) in the presence of PhCN or PhH results in indiscriminate reactions that do not produce tractable products. In contrast, reduction of [PtCl2(dcpp)] in CH3CN/C6H6/Bu4NClO4 produces [PtHPh(dcpp)] with considerable selectivity via aromatic C-H activation by [Pt(dcpp)]. At room temperature the complex [PtHPh(dcpp)] undergoes exchange with C6D6 to generate [PtD(C6D5)(dcpp)].