[PtCl(η2-styrene)(N,N,N',N'-tetramethyl-1,2-ethanediamine)](ClO4) | 158782-44-6

• 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: [PtCl(η2-styrene)(N,N,N',N'-tetramethyl-1,2-ethanediamine)](ClO4)
• 英文别名: [(N,N,N',N'-tetramethylethylenediamine)PtCl(η2-styrene)][ClO4]；[PtCl(η2-styrene)(N,N,N',N'-tetramethylethylenediamine)](ClO4)；[PtCl(η2-CH2CHC6H5)(tmeda)](ClO4)；[(tmeda)PtCl(η2-CH2CHPh)][ClO4]；[PtCl(η2-styrene)(tmeda)](ClO4)；chloroplatinum(1+);styrene;N,N,N',N'-tetramethylethane-1,2-diamine;perchlorate
• CAS: 158782-44-6
• 化学式: C₁₄H₂₄ClN₂Pt*ClO₄
• 分子量: 550.342
• InChiKey: UPYMEHWJOVMHRJ-UHFFFAOYSA-L

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：

  [PtCl(η2-styrene)(N,N,N',N'-tetramethyl-1,2-ethanediamine)](ClO4) 在 sodium carbonate 作用下， 以 氯仿 为溶剂， 以80%的产率得到E-[PtCl(η2-CHCHC6H5)(tmeda)]
  参考文献：
  名称：

  铂 (II) 配位球中的乙烯基去质子化：烯基配合物的区域选择性形成

  摘要：

  [PtCl(η2-CH2=CHAr)(tmeda)](ClO4) (1) [Ar = C6H5 (1a), 4-CH3OC6H4 (1b), 3-NO2C6H4 (1c); tmeda = N,N,N',N'-四甲基乙二胺）与三乙胺，甚至无机碳酸盐，导致乙烯质子的提取和（烯基）铂物质的形成 [PtCl{(E)-CH=CHAR }(tmeda)] (2) 高产。最初形成的 (E) 异构体在氯化溶剂溶液中部分异构化为 (Z) 形式 [平衡比 (E)/(Z) ≈ 4:1]；异构化反应较慢，由可见光催化。苯基取代基（给电子体 OMe 或吸电子 NO2 基团）的性质似乎不会影响去质子化的速率。已通过 1D 和 2D 1H 和 13C NMR 光谱阐明了所形成的（烯基）铂物种的性质和立体化学。

  DOI：

  10.1002/ejic.200400512
• 作为产物：
  描述：

  苯乙烯 、 [(N,N,N',N'-tetramethylethylenediamine)PtCl(η2-propene)][ClO4] 以 二氯甲烷 为溶剂， 以90%的产率得到[PtCl(η2-styrene)(N,N,N',N'-tetramethyl-1,2-ethanediamine)](ClO4)
  参考文献：
  名称：

  铂 (II) 配位球中的乙烯基去质子化：烯基配合物的区域选择性形成

  摘要：

  [PtCl(η2-CH2=CHAr)(tmeda)](ClO4) (1) [Ar = C6H5 (1a), 4-CH3OC6H4 (1b), 3-NO2C6H4 (1c); tmeda = N,N,N',N'-四甲基乙二胺）与三乙胺，甚至无机碳酸盐，导致乙烯质子的提取和（烯基）铂物质的形成 [PtCl{(E)-CH=CHAR }(tmeda)] (2) 高产。最初形成的 (E) 异构体在氯化溶剂溶液中部分异构化为 (Z) 形式 [平衡比 (E)/(Z) ≈ 4:1]；异构化反应较慢，由可见光催化。苯基取代基（给电子体 OMe 或吸电子 NO2 基团）的性质似乎不会影响去质子化的速率。已通过 1D 和 2D 1H 和 13C NMR 光谱阐明了所形成的（烯基）铂物种的性质和立体化学。

  DOI：

  10.1002/ejic.200400512

文献信息

• A NMR, X-ray, and DFT combined study on the regio-chemistry of nucleophilic addition to platinum(II) coordinated terminal olefins
  作者：Carmen R. Barone、Renzo Cini、Eric Clot、Odile Eisenstein、Luciana Maresca、Giovanni Natile、Gabriella Tamasi

  DOI：10.1016/j.jorganchem.2008.05.040

  日期：2008.8

  1g; tmeda = N,N,N′,N′-tetramethyl-1,2-ethanediamine) has been considered. In the styrene complex (1b) both solution (NMR) and solid state (X-ray) data indicate a significant difference in the Pt–C bond lengths (the longer bond being that involving the olefin carbon atom carrying the phenyl ring). Such a difference increases when X is an electron donor group (EDG, 1c) and decreases when X is an electron

  该系列铂络合物[氯铂酸（η的2 -CH 2 CH-C 6 H ^ 4 -X）乙二胺（TMEDA）]（CLO 4）（X = H，1B ; 4- OME，1C ; 3-OME，1D ; 4 -CF 3，1E ; 3-CF 3，1F ; 3-NO 2，1克; TMEDA =  ñ，ñ，ñ '，ñ '，N'-四甲基-1,2-乙二胺）已被考虑。在苯乙烯络合物中（1b）溶液（NMR）和固态（X射线）数据均表明Pt-C键长存在显着差异（较长的键是涉及带有苯环的烯烃碳原子的键）。当X是电子给体基团（EDG，1c）时，这种差异增大，而当X是电子吸收基团（EWG，1d - g）时，这种差异减小。亲核试剂（MEO的攻击- ）与取代的碳（马氏型，M）是迄今为止最有利于在未取代的（的情况下1B）或EDG取代的（1C）的苯乙烯。EWG（化合物1d - g）的存在使M和抗-M类型的攻击。还对1b，c和1e进行了DFT计
• Aiding Factors in the Formation of Azaplatinacyclobutane Rings – X‐ray and Crystal Structure of [Pt{CH(Ph)CH ₂ NEt ₂ ‐κC,κN}( <i>N</i> , <i>N</i> , <i>N′</i> , <i>N′</i> ‐tetramethylethylenediamine)] ⁺ and of Its Open‐Chain Precursor
  作者：Giuseppe Lorusso、Carmen R. Barone、Nicola G. Di Masi、Concetta Pacifico、Luciana Maresca、Giovanni Natile

  DOI：10.1002/ejic.200601219

  日期：2007.5

  The addition products 2 of a secondary amine to a coordinated olefin, in the cationic complexes [PtCl(η2-CH2=CHR)(tmeda)]+ (tmeda = N,N,N′,N′-tetramethylethylenediamine; R = Me, 1a; Ph, 1b, H, 1c), undergo in basic medium an intramolecular nucleophilic substitution with elimination of the chlorido ligand and formation of an azaplatinacyclobutane ring 3. The ring-closing process occurs notwithstanding

  仲胺与配位烯烃的加成产物 2，在阳离子络合物 [PtCl(η2-CH2=CHR)(tmeda)]+ (tmeda = N,N,N',N'-四甲基乙二胺；R = Me， 1a; Ph, 1b, H, 1c)，在碱性介质中进行分子内亲核取代，消除氯配体并形成氮杂铂环丁烷环 3. 闭环过程发生，尽管没有不稳定的配体转移到离开氯配体和氨基-乙炔链上的大取代基。如果加成产物 2 是马尔科夫尼科夫异构体和反马尔科夫尼科夫异构体的混合物，则反马尔科夫尼科夫形式的闭环反应更快，这导致环化物种中反马尔科夫尼科夫异构体的相对量增加3. 两种异构体之间氮杂铂环丁烷环形成速率的差异已被解释为基于在反马尔科夫尼科夫形式的情况下更有利的立体化学。[PtCH(Ph) NEt2-κC,κN}(tmeda)]+ (3bn) 及其开链前体 [PtClCH(Ph) NHEt2}(tmeda)]+ 的 X 射线晶体结构(20
• Fanizzi, Francesco P.; Maresca, Luciana; Natile, Giovanni, Gazzetta Chimica Italiana, 1994, vol. 124, # 3, p. 137 - 142
  作者：Fanizzi, Francesco P.、Maresca, Luciana、Natile, Giovanni、Pacifico, Concetta

  DOI：——

  日期：——
• Phase dependent η2-alkene versus η1-alkyl transformation in platinum(II) complexes
  作者：Luciana Maresca、Giovanni Natile

  DOI：10.1016/s0020-1693(98)00345-4

  日期：1999.2

  Addition products of some nucleophiles to the coordinated olefin in [Pt(eta(2)-olefin)Cl(tmen)](+) (1) (tmen = N,N,N',N'-tetramethylethylenediamine) have shown to undergo a chemical transformation in the solid phase. The acetylacetonate (acac) addition product [PtCH(H,Ph)CH(Ph,H)(acac)}Cl(tmen)] (2) is formed as a mixture of Marcovnikov and anti-Marcovnikov isomers; in the solid state slow isomerization to the pure Marcovnikov isomer takes place. The complex [PtCH2CH2OC(O)CH3}Cl(tmen)] (3), obtained by addition of acetate anion to 1, in the solid state slowly dissociates into its constituent species. Heterometallacycles [PtCH(H,Me)CHMeONO}(tmen)](+) (4) formed by endo nucleophilic attack of an oxygen of the nitro Ligand on the cis alkene ligand can be detected in solution; however, they lose stability in the solid state where they revert to the acyclic species. The hydroxyl compound [Pt(CH2CH2OH)Cl(tmen)] (5), formed by addition of OH- to 1, undergoes, in the solid state, a condensation reaction to give the dimeric ether species [(tmen)ClPtCH2CH2OCH2CH2PtCl(tmen)] (6) and a water molecule. Moreover, the 5 to 6 transformation is catalyzed by carbon dioxide. All data are in accord with the solid state increasing the stability of the eta(2)-olefin species and free nucleophile over the eta(1)-alkyl addition product, a role for enthropic factors is envisaged. (C) 1999 Elsevier Science S.A. All rights reserved.