cis-dibromo[1,1'-methylenebis[1,1-diphenylphosphine-κP]]platinum | 64040-31-9

• 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: cis-dibromo[1,1'-methylenebis[1,1-diphenylphosphine-κP]]platinum
• 英文别名: platinum(II)dibromo((diphenylphosphine)2(CH2)) complex；[PtBr2(bis(diphenylphosphino)methane)]；{Pt(dppm)Br2}；[PtCl2(dppm)]；cis-[PtBr2(1,1'-(methylene-1,3-diyl)bis[1,1-diphenylphosphine])]；cis-[PtBr2(1,3-bis(diphenylphosphino)methane)]；dibromoplatinum;diphenylphosphanylmethyl(diphenyl)phosphane
• CAS: 64040-31-9
• 化学式: C₂₅H₂₂Br₂P₂Pt
• 分子量: 739.285
• InChiKey: WUHUDGLLRJYDPE-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  6.9
• 重原子数：
  30.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  重氮甲烷 、 cis-dibromo[1,1'-methylenebis[1,1-diphenylphosphine-κP]]platinum 以 乙醚 、 二氯甲烷 为溶剂， 以65%的产率得到{Pt(CH₂Br)2((C₆H₅)2PCH₂P(C₆H₅)2)}
  参考文献：
  名称：

  [Pt（CH 2 X）2（Ph 2 PCH 2 PPh 2 - PP '）]（X = Cl，Br或I）的反应性：四元至五元环膨胀。[双（二苯基膦基）-甲烷-PP ']双（氯甲基）铂（II）的晶体结构

  摘要：

  将CH 2 N 2添加到螯合物[ PtX 2（dppm- PP '）]（X = Cl，Br或I; dppm = Ph 2 PCH 2 PPh 2）得到配合物[Pt（CH 2 X）2（ dppm- PP '）]（2a）–（2c）已被充分表征。已确定[Pt（CH 2 Cl）2（dppm- PP '）]（2a）的X射线晶体结构以确认其化学同一性（正交晶系，空间群Pbca，对于2499次观察到的反射，R = 0.053 [我/σ（我）2.0]。向配合物（2a）中加入HCl，得到[PtCl（CH 2 Cl）（dppm- PP '）]（3）。用膦或吡啶处理（2a）导致扩环反应，得到[PtL（CH 2 Cl）（CH 2 PPh 2 CH 2 PPh 2）] Cl [L =吡啶（4a），PPh 3（4b） ，或PPh 2 H（4c）]。dppm（2a）给出双螯合物[Pt（CH 2 PPh 2 CH 2 PPh2）

  DOI：

  10.1039/dt9900001553
• 作为产物：
  描述：

  [PtBr2(bis(diphenylphosphino)methane)] dichloromethane solvate 以 neat (no solvent) 为溶剂， 生成 cis-dibromo[1,1'-methylenebis[1,1-diphenylphosphine-κP]]platinum
  参考文献：
  名称：

  Brown, Michael P.; Puddephatt, Richard J.; Rashidi, Mehdi, Journal of the Chemical Society, Dalton Transactions

  摘要：

  DOI：

文献信息

• Tin(II) Halide Insertion or Halogen Exchange in the Reactions of Dihaloplatinum(II) Complexes with Tin(II) Halide
  作者：Badri Z. Momeni、Hoori Kazmi、Atefeh Najafi

  DOI：10.1002/hlca.201100045

  日期：2011.9

  in equilibrium with the starting complex cis‐[PtBr2(dppm)]. Moreover, the reaction of cis‐[PtCl2(dppb)] with a mixture SnCl2/SnI2 in a 2 : 1 mol ratio resulted in the formation of cis‐[PtI2(dppb)] as a consequence of the selective halogen‐exchange reaction. 31P‐NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono‐

  SnCl 2与配合物顺式-[PtCl 2（P 2）]（P 2 = dppf（1,1'-双（二苯基膦基）二茂铁），dppp（1,3-双（二苯基膦基）丙烷= 1,1 ′-（丙烷-1,3-二基）双[1,1-二苯基膦]），dppb（1,4-双（二苯基膦基）丁烷= 1,1'-（丁烷-1,4-二苯基）双[1 ，1-二苯基膦]）和dpppe（1,5-双（二苯基膦基）戊烷= 1,1'-（戊烷-1,5-二基）双[1,1-二苯基膦]））导致SnCl的插入2进入PtCl键，得到顺式[[PtCl（SnCl 3）（P 2）]配合物。但是，配合物顺式[PtCl 2（P2）]（P 2 = dppf，dppm（双（二苯基膦基）甲烷= 1,1'-亚甲基双[1,1-二苯基膦]），dppe（1,2-双（二苯基膦基）乙烷= 1,1'-（乙烷1,2-二基）双[1,1-二苯基膦]），dppp，dppb和dpppe; P = Ph 3
• Bismuth–Halide Oxidative Addition and Bismuth–Carbon Reductive Elimination in Platinum Complexes Containing Chelating Diphosphine Ligands
  作者：S. Masoud Nabavizadeh、Fatemeh Niroomand Hosseini、Negar Nejabat、Zahra Parsa

  DOI：10.1021/ic4018745

  日期：2013.12.2

  (1a, P–P = dppm; 1b, P–P = dppe), occurs easily to yield a mixture of platinum(II) complexes [PtMeX(P–P)], 2, and [PtX2(P–P)], 3, and the binuclear complex [Pt2Me2(μ-X)(μ-dppm)2]X, 4. On the basis of 31P NMR and UV–vis spectroscopy, a mechanism is proposed in which the rate determining step is conversion of the yellowish Pt(II)-BiX3 adduct BiI3·[PtMe2(dppm)], A, into the Pt(IV)–Bi(III) intermediate

  BiX 3（X = Cl，Br，I）与[PtMe 2（P–P）]（1a，P–P = dppm; 1b，P–P = dppe）的反应容易发生，从而生成铂的混合物（II）络合物[PtMeX（P–P）]，2和[PtX 2（P–P）]，3和双核络合物[Pt 2 Me 2（μ-X）（μ-dppm）2 ] X ，4。基于31 P NMR和紫外可见光谱，提出了一种机制，其中速率确定步骤是微黄色的Pt（II）-BiX 3加合物BiI 3 ·[PtMe 2（dppm）]，A，进入Pt（IV）–Bi（III）中间体[PtMe 2（BiX 2）X（P–P）]，IM1。密度泛函理论（DFT）研究表明，中间体IM1可能在丙酮溶液中形成，该丙酮溶液在形成配合物2和3之前要经过Bi-C还原消除过程。中间体IM1的结构在理论上使用DFT计算确定。在稀丙酮溶液中，通过紫外-可见光谱监测，氧化加成过程遵循一级动力学。对于较重的卤化物，总体反应较慢。
• Bis[bis(diphenylphosphino)methane]platinum(II) salts: evidence for the formation of a five-co-ordinate bis[bis(diphenylphosphino)methane]-halogenoplatinum(II) cation
  作者：Martin C. Grossel、Roger P. Moulding、Kenneth R. Seddon、Fiona J. Walker

  DOI：10.1039/dt9870000705

  日期：——

  The salts [Pt(dppm)2]X2(X = Cl, Br, I, PF6 or BPh4; dppm = Ph2PCH2PPh2) have been studied in solution by 1H, 31P, and 195Pt n.m.r. spectroscopy and by conductivity measurements. The halide salts are believed to form the five-co-ordinate cation [Pt(dppm)2X]+ in solution.

  盐[Pt（dppm）2 ] X 2（X = Cl，Br，I，PF 6或BPh 4； dppm = Ph 2 PCH 2 PPh 2）已在溶液中以1 H，31 P和195 Pt进行了研究。核磁共振光谱和电导率测量。据信卤化物盐在溶液中形成五配位阳离子[Pt（dppm）2 X] +。
• Diastereoselective carbene insertions into platinum-halogen bonds. Crystal structure of [PtCl(R-CHClCO2Et)(R,R-diop)]
  作者：Paola Bergamini、Emiliana Costa、Silvana Sostero、A. Guy Orpen、Paul G. Pringle

  DOI：10.1021/om00059a062

  日期：1992.11

  Ethyl diazoacetate reacts with [PtX2L2] [X = Cl, Br, 1; L2 = 1,5-cyclooctadiene (cod), 2 PPh3, Ph2P-(CH2)nPPh2, n = 1 (dppm), 2 (dppe), 3 (dppp), 4 (dppb)] to give the corresponding [PtX(CHXCO2Et)L2] as a racemic mixture in high yields. The cod ligands in [PtX(CHXCO2Et)(cod)] are readily displaced by PPh3 or diphosphines. When optically active complexes [PtX2L*] (X = Cl, I; L* = R,R-diop, S,S-chiraphos, S,S-skewphos) were treated with ethyl diazoacetate, the products (PtX(CHXCO2Et)L*] were mixtures of diastereoisomers in different proportions. The major diastereoisomer of [PtCl(CHClCO2Et)(R,R-diop)] was readily separated by fractional crystallization, and its crystal structure revealed that the configuration at the alpha-carbon was R. This compound is configurationally stable for at least 14 d in CDCl3 solution as shown by P-31 NMR spectroscopy. Treatment of pure [PtCl(CHClCO2Et)(R,R-diop)] with S,S-skewphos led to exchange of diphosphines and thereby the assignment of the S configuration at the alpha-carbon of the major product of the reaction of [PtCl2(S,S-skewphos)] with ethyl diazoacetate. With the aim of optimizing the diastereoselectivity of the insertion reaction, the chiral diazo ester N2CHCO2R (R = R,R-menthyl) was used as the reagent but it was found that the diastereoselectivities were similar to those with N2CHCO2Et. The highest diastereoselectivities (up to 7:1) were obtained with N2CHCOPh.
• Irisli, Sevil; Sarikahya, Yueksel, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 1995, vol. 25, p. 965 - 976
  作者：Irisli, Sevil、Sarikahya, Yueksel

  DOI：——

  日期：——