trans-chloro(triphenylsilyl)bis(dimethylphenylphosphine)platinum(II) | 31388-57-5

• 英文名称: trans-chloro(triphenylsilyl)bis(dimethylphenylphosphine)platinum(II)
• 英文别名: trans-chlorobis(dimethylphenylphosphine)(triphenylsilyl)platinum(II)；trans-[PtCl(PMe2Ph)2(SiPh3)]；trans-Pt(PMe2Ph)2(SiPh3)Cl；trans-PtCl(SiPh3)(PMe2Ph)2
• CAS: 31388-57-5；25930-50-1；26709-54-6
• 化学式: C₃₄H₃₇ClP₂PtSi
• 分子量: 766.234
• InChiKey: OZIABLOSPBHRCZ-UHFFFAOYSA-M

计算性质

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

反应信息

• 作为反应物：
  描述：

  trans-chloro(triphenylsilyl)bis(dimethylphenylphosphine)platinum(II) 在 MeOH 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 cis-Pt(SiMe2Ph)(SiPh3)(PMe2Ph)2
  参考文献：
  名称：

  Mechanistic Study on the Insertion of Phenylacetylene into cis-Bis(silyl)platinum(II) Complexes

  摘要：

  Four bis(silyl)platinum complexes cis-Pt(SiR3)(2)(PMe2Ph)(2) (SiR3 = SiMe2Ph (la), SiMePh2 (Ib), SiPh3 (Ic), SiFPh2 (Id)) have been prepared and their reactions with alkynes and alkenes examined. The X-ray structures of 1a-c exhibit significant distortion from the square planar geometry in the order Ib > Ic > la. Complexes 1a-d react with phenylacetylene in solution to give the corresponding insertion complexes cis-Pt{C(Ph)=CH(SiR3)}(SiR3)(PMe2Ph)(2) (2a-d). Complex Ic reacts also with acetylene to afford the insertion complex cis-Pt(CH=CHSiPh3)(SiPh3)(PMe2Ph)(2) (2e), whose structure has been determined by X-ray diffraction study. Kinetic studies indicate the insertion process involving prior dissociation of PMe2Ph ligand from 1, followed by insertion of phenylacetylene into the Pt-SiR3 bond. The reactivity toward insertion decreases in the order Ic > la > Ib much greater than Id. Factors responsible for the reactivity order are discussed on the basis of kinetic data and X-ray structures.

  DOI：

  10.1021/om980610w

文献信息

• 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。
• Reactions of <i>cis</i>- and <i>trans</i>-Silyl(methyl)platinum(II) Complexes with Phenylacetylene. Remarkable Effect of Cis and Trans Configurations on the Reactivity
  作者：Fumiyuki Ozawa、Toshihiko Hikida

  DOI：10.1021/om960506j

  日期：1996.10.15

  (3b), respectively). In contrast, trans-PtMe(SiPh3)L2 complexes (L = PMe2Ph (2a), PMePh2 (2b)) were totally inactive toward acetylene insertion. The cis-organo(silyl)platinum complexes cis-PtMe(SiPh3)(PMe3)(PMePh2) (1c) and cis-Pt(COEt)(SiPh3)(PMe2Ph)2 (6d) also underwent the insertion of phenylacetylene into the Pt−SiPh3 bond to provide quantitative yields of cis-PtMeC(Ph)CH(SiPh3)}(PMe3)(PMePh2)

  甲硅烷基（甲基）铂配合物的顺式和反式-PtMe（SiPh 3）L 2（L = PMe 2 Ph，PMePh 2）的两个几何异构体表现出完全不同的对苯乙炔的反应性。的反应顺-PtMe（SIPH 3）L- 2（L = PME 2 Ph（上1A），PMePh 2（图1b）），与苯乙炔在室温下于苯容易进行，得到乙炔插入产品顺-PtMe C（PH ）CH（SiPh 3）} L 2（L = PMe 2 Ph（3a），PMePh 2（3b）。相反，反式-PtMe（SiPh 3）L 2络合物（L = PMe 2 Ph（2a），PMePh 2（2b））对乙炔插入完全无效。所述顺式-organo（甲硅烷基）铂络合物的顺-PtMe（SIPH 3）（PME 3）（PMePh 2）（1C）和顺式-Pt（COET）（SIPH 3）（PME 2 PH）2（6D）还对Pt-SiPh 3键插入了苯乙炔以提供定量的顺式-PtMe
• Preparation and C−Si Reductive Elimination Behavior of <i>cis</i>-Alkynyl(silyl)platinum(II) Complexes
  作者：Fumiyuki Ozawa、Takuya Mori

  DOI：10.1021/om0302701

  日期：2003.8.1

  cis-alkynyl(silyl)platinum(II) complexes, cis-Pt(C⋮CAr)(SiAr‘3)(PMe2Ph)2 (2:  Ar = Ph, 4-MeOC6H4, 4-MeC6H4, 4-ClC6H4, 4-BrC6H4, 4-NCC6H4; Ar‘ = Ph, 4-MeOC6H4, 4-MeC6H4, 4-CF3C6H4), have been prepared, and their thermolysis reactions in solution have been examined. Complexes 2 smoothly undergo C−Si reductive elimination in benzene-d6 at around 35 °C to give the corresponding platinum(0) complexes coordinated

  一系列的顺式-炔基（甲硅烷基）铂（II）络合物，顺式-Pt（C⋮CAR）（SIAR” 3）（PME 2 PH）2（2：Ar为PH，4-MeOC 6 H ^ 4，4-的MEC 6 ħ 4，4-CLC 6 ħ 4，4- BRC 6 ħ 4，4-NCC 6 ħ 4 ;中，Ar” =苯基，4- MeOC 6 ħ 4，4-MEC 6 ħ 4，4-CF 3 ç 6高4），已经制备，并检查了它们在溶液中的热分解反应。配合物2顺利经历苯C-硅还原消除d 6在约35℃下，得到相应的铂配位silylacetylenes（0）络合物，Pt（ARC⋮CSiAr” 3）（PME 2 PH）2（3）。动力学检查表明协同反应过程可直接从四坐标复合体开始操作。Ar和Ar'基团上的供电子基更多的取代基可提供更高的还原消除速率。
• C−Si Reductive Elimination from <i>cis</i>-Vinyl(silyl)platinum(II) Complexes
  作者：Fumiyuki Ozawa、Toshikazu Tani、Hiroyuki Katayama

  DOI：10.1021/om0580001

  日期：2005.5.1

  The complexes cis-Pt(CHCH2)(SiR3)(PMe2Ph)2 (SiR3 = SiPh3 (3a), Si(C6H4Me-p)3 (3b), Si(C6H4OMe-p)3 (3c), SiMePh2 (3d), SiFPh2 (3e)) have been prepared by the reactions of trans-PtCl(SiR3)(PMe2Ph)2 with Mg(CHCH2)2 in THF, followed by trans−cis isomerization of the resulting trans-alkenyl(silyl) complexes in solution promoted by CO. Complexes 3a−e undergo C−Si reductive elimination in toluene-d8 to give

  配合物顺式-Pt（CH CH 2）（SiR 3）（PMe 2 Ph）2（SiR 3 = SiPh 3（3a），Si（C 6 H 4 Me- p）3（3b），Si（C 6 H通过反式-PtCl（SiR 3）（PMe 2）的反应制备了4 OMe- p）3（3c），SiMePh 2（3d），SiFPh 2（3e））。PH）2用Mg（CH CH 2）2在THF中，然后将所得的反式-顺式异构化的反式-烯基（甲硅烷基）在溶液中的复合物由CO配合物促进。图3a - ê经历甲苯C-硅还原消除d 8得到与乙烯基硅烷配位的铂（0）配合物。动力学数据表明，没有膦配体解离的直接反应路径。
• Thermolysis Reactions of <i>cis</i>-PtR(SiPh₃)(PMe₂Ph)₂ in Solution
  作者：Koh Hasebe、Jun Kamite、Takuya Mori、Hiroyuki Katayama、Fumiyuki Ozawa

  DOI：10.1021/om000012t

  日期：2000.5.1

  A series of trans- and cis-PtR(SiPh3)(PMe2Ph)(2) complexes have been prepared and their thermolysis reactions in solution examined. The trans isomers (R = Me, Et) are robust, and only the methyl complex affords MeSiPh3 as the reductive elimination product in 72-82% yields. In contrast, the cis isomers (R = Me, Et, Pr, Bu) form the corresponding alkylsilanes in almost quantitative yields (>97%). Despite the selective formation of the reductive elimination products, the cis-alkyl-silyl complexes bearing beta-hydrogens undergo a rapid repetition of the beta-hydrogen elimination and insertion processes, as confirmed by a deuterium-labeling experiment using cis-Pt(CH2CD3)(SiPh3)(PMe2Ph)(2). The alkylsilane formation from the cis isomers proceeds via two reaction paths. One is the direct C-Si reductive elimination. On the other path, the cis-PtR(SiPh3)(PMe2Ph)(2) complexes are initially isomerized to the corresponding cis-PtPh(SiRPh2)(PMe2Ph)(2) complexes by the exchange of the Pt-R group with the Si-Ph group, and the resulting phenyl-silyl complexes reductively eliminate alkylsilanes. The methyl-silyl complex decomposes exclusively by the former path, while the other alkyl-silyl complexes (R = Et, Pr, Bu) follow mainly the latter path. Preparation and thermolysis reaction of the related cis-PtEt(GePh3)(PMe2Ph)(2) are also reported.