trans-[PtBr2(PMe2Ph)2] | 40791-54-6

• 英文名称: trans-[PtBr2(PMe2Ph)2]
• 英文别名: dibromobis(dimethylphenylphosphine)platinum(II)
• CAS: 40791-54-6；29143-70-2；15616-81-6
• 化学式: C₁₆H₂₂Br₂P₂Pt
• 分子量: 631.186
• InChiKey: LRKZQMAYQBRXEK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  trans-[PtPh(O3SCF3)(PMe2Ph)2] 以 四氢呋喃 、 二氯甲烷 、 二氯甲烷-D2 为溶剂， 生成 trans-[PtBr2(PMe2Ph)2] 、 trans-[PtPhBr(PMe2Ph)2] 、 trans-[PtPh2(PMe2Ph)2] 、 cis-platinum(II)Ph2(PMe2Ph)2
  参考文献：
  名称：

  Reaction Mechanism of Transmetalation between Tetraorganostannanes and Platinum(II) Aryltriflate Complexes. Mechanistic Model for Stille Couplings

  摘要：

  The complexes trans-[PtPh(OTf)(PMe2Ph)(2)] (1) and trans- [PtPh(OTf)(PPh3)(2)] (4) were synthesized from the corresponding chloro complexes in moderate yields. Complex I is slowly hydrolyzed in solution, giving the dinuclear hydroxo-bridged complex [Pt(mu-OH)(PMe2Ph)(2)](2)(CF3SO3)(2) (6), which was characterized by X-ray crystallography. In solution I and 4 undergo fast solvolysis to give the corresponding solvento cations. The reactivities of 1 and 4 with Me3SnPh were investigated in different solvents, and with 1 two products, trans- [PtPh2(PMe2Ph)(2)] (8) and cis-[PtPh2(PMe2Ph)(2)] (9), were always formed simultaneously. In THF an intermediate, trans- [PtPhMe(PMe2Ph)(2)] (14), was characterized on the path to 9. The kinetics for these reactions were evaluated numerically, and on the basis of rate laws, activation parameters, and reactivity trends a mechanism involving parallel equilibria to 8 and 9 with associative activation in all steps is proposed. In this mechanism the initial attack always takes place trans to the phenyl group, giving 8 and 14, respectively, via an open transition state. In a subsequent reaction, 14 reacts with another molecule of stannane, giving 9 as the final product via a cyclic transition state. Complex 4 gives exclusive formation of cis products: cis-[PtPhMe(PPh3)2] (12) and cis-[PtPh2(PPh3)2] (13). These results are discussed in relation to the reaction mechanism of the transmetalation step in the Stille reaction.

  DOI：

  10.1021/om051021a

文献信息

• Unsaturated σ-hydrocarbyl transition-metal complexes. Part 2. Synthesis and reactions of vinylplatinum complexes and a comparison with analogous fluorovinyl and alkynyl complexes
  作者：Christine J. Cardin、David J. Cardin、Michael F. Lappert

  DOI：10.1039/dt9770000767

  日期：——

  cis-[PtRL2(SnMe3)]. When the latter complex (R = CHCH2) reacts with X2 or MeX further oxidative addition occurs exclusively at the platinum centre. Aromatic isonitriles (R′NC)co-ordinate to the platinum and give insertion products trans-[PtC(CHCH2)= NR′}ClL2] on heating or carbene complexes with NBunH2. The alkynyl trans-[Pt(CCPh)ClL2] also forms 1 :1 adducts with R′NC and carbene complexes therefrom, but no insertion

  三甲基锡的烯基（CH CH 2或CF CF 2）或炔基（C CPh）衍生物在通过复分解合成相应的单有机铂（II）物种方面优于锂或镁试剂（L = SnMe 3 R +顺式-[PtCl 2 L 2 ] →反式-[PtRClL 2 ] + SnMe 3 Cl叔膦）。SnMe 3 R的反应顺序为R = C CPh> CF CF 2 > CH CH 2。还发现该顺序用于氧化添加SnMe 3R至Pt 0给出顺式-[PtRL 2（SnMe 3）]。当后者的络合物​​（R = CH CH 2）与X 2或MeX反应时，进一步的氧化加成仅在铂中心发生。芳香异腈（R'NC）与铂配位，并在加热或带有NBu n H 2的卡宾配合物中得到插入产物反式-[Pt C（CH CH 2）= NR'} ClL 2 ] 。炔基反式-[Pt（C CPh）ClL 2]也与R'NC和卡宾配合物形成1：1加合物，但没有插入产物。给出了新配合物的光谱数据。
• Reactions of methyl fluorosulphate and triethyloxonium tetrafluoroborate with transition-metal complexes
  作者：Colin Eaborn、Nicholas Farrell、James L. Murphy、Alan Pidcock

  DOI：10.1039/dt9760000058

  日期：——

  Reactions of SFO2(OMe) and [Et3O][BF4] with a variety of transition-metal complexes have been examined and classified as ligand abstraction, oxidative additions, oxidation, ligand alkylation, or reactions in which an anion fragment is abstracted from a ligand. Factors influencing the mode of reaction and the mechanisms of some of the reactions are discussed.

  已经检查了SFO 2（OMe）和[Et 3 O] [BF 4 ]与多种过渡金属配合物的反应，并将其分类为配体抽象，氧化加成，氧化，配体烷基化或其中阴离子片段为从配体中提取。讨论了影响反应方式的因素和某些反应的机理。
• Some palladium(II) and platinum(II) derivatives of pentaborane(9)
  作者：Norman N. Greenwood、John D. Kennedy、John Staves

  DOI：10.1039/dt9780001146

  日期：——

  palladium(II) and platinum(II) halides affords cis-[M(B5H8)(PR3)2X] in good yields (X = Cl, Br, I, or Me; PR3= PPh3, PMe2Ph, PMe3, or ½Ph2PCH2CH2PPh2). The platinum complexes are more stable than those of pailadium and can be stored unchanged for long periods at room temperature. Similar reactions with appropriate starting materials lead to cis-[Pt(B5H8)Cl(AsPh3)2], cis-[Pt(B5H8)(PMe2Ph)(µ-SMe)}2], and the

  碘化-八氢五硼酸钾K [B 5 H 8 ]与钯（II）和卤化铂（II）的许多顺式-双（膦）配合物复分解得到顺式-[M（B 5 H 8）（PR 3）2 X]以良好的收率（X =氯，溴，I，或Me; PR 3 = PPH 3，PME 2 PH，PME 3，或½Ph 2 PCH 2 CH 2 PPH 2）。铂配合物比钯配合物更稳定，并且可以在室温下长时间不变地保存。使用适当的原料进行的类似反应会生成顺式[[Pt（B 5 H 8）Cl（AsPh 3）2 ]，顺式[[Pt（B 5 H 8）（PMe 2 Ph）（µ-SMe）} 2 ]。 ，以及不太稳定的反式-[Pt（B 5 H 8）I（PMe 2 Ph）2 ]和反式-[Pt（B 5 H 8）Me（PMe 2 Ph）2]。在所有情况下，乙5 ħ 8配体为η 2键合的与金属经由两个基底硼原子B（2）和B（3）的。氢-1，11 B，31 P，和195的Pt
• Redistribution reactions of platinum(II) and palladium(II) phosphine complexes
  作者：Jeffrey A. Rahn、Mark S. Holt、John H. Nelson

  DOI：10.1016/s0277-5387(00)86441-4

  日期：1989.1

  Abstract Anion redistribution equilibria of the type (R 3 P) 2 MX 2 + (R 3 P) 2 MY 2 ⇆ 2(R 3 P) 2 MXY (X, Y = Cl, Br, I, CN, N 3 ; R 3 P = Me 2 PhP, MePh 2 P, (Bzl) 3 P, (CH 2 CH) 2 PhP, (CH 2 CH)Ph 2 P and 1-phenyl-3,4-dimethylphosphole; M = Pd, Pt) have been studied by 31 P 1 H} and in some cases 195 Pt 1 H} NMR spectroscopy. It was found that except for the two cases when R 3 P = MePh 2 P, M

  摘要（R 3 P）2 MX 2 +（R 3 P）2 MY 2⇆2（R 3 P）2 MXY（X，Y = Cl，Br，I，CN，N 3; R 3 P = Me 2 PhP，MePh 2 P，（Bzl）3 P，（CH 2 = CH）2 PhP，（CH 2 = CH）Ph 2 P和1-苯基-3,4-二甲基磷脂; M = Pd， Pt）已通过31 P 1 H}和某些情况下的195 Pt 1 H} NMR光谱进行了研究。发现除了两种情况，当R 3 P = MePh 2 P，M = Pd，X = Cl，Y = Br和R 3 P = Me 2 PhP，M = Pd，X = Cl，Y = Br时，重新分配通常是瞬时的。（R 3 P）2 PdCl 2 +（R 3 P）2 Pd（CN）2反应较慢，但已完成。相反，当一个阴离子为CN-时，即使一个月后，铂络合物也未观察到阴离子再分布。混合阴离子物质相对于对称物
• Some cyclopropylplatinum complexes
  作者：Ralph L. Phillips、Richard J. Puddephatt

  DOI：10.1039/dt9780001732

  日期：——

  decomposition of some of these complexes have been identified. The complex trans-[Pt([graphic omitted]H2)Cl(PMe2Ph)2] reacts with Ag[NO3] and K[PF6] to give the (1–3-η-allyl)platinum complex [ Pt(η-C3H5)(PMe2Ph)2][PF6], and the corresponding 1-deuteriocyclopropylplatinum complex gives the (1–3-η-2-deuterioallyl) platinum complex.

  由顺式-[PtCl 2（PMe 2 Ph）2 ]和环丙基-锂制备了环丙基铂配合物顺式-[Pt（H 2）2（PMe 2 Ph）2 ] 。它反应用碘甲烷得到[铂（[图形省略1 H 2）2我（我）（PME 2 PH）2 ]。用烯丙基溴或苄基溴制得[PtBr 2（[图省略] H 2）2（PMe 2 Ph）2），并用HCl制得反式-[Pt（[省略图示] H 2）Cl（PMe 2 Ph）2 ]。已经确定了其中一些配合物的热分解产物。复杂的反式-[Pt（H）2 Cl（PMe 2 Ph）2 ]与Ag [NO 3 ]和K [PF 6 ]反应，生成（1-3-η-烯丙基）铂络合物[的Pt（η-C 3 H ^ 5）（PME 2 PH）2 ] [PF 6 ]和相应的1- deuteriocyclopropylplatinum复杂给出了（1-3-η-2- deuterioallyl）铂配合物。