chloro(4,4'-di-tert-butyl-2,2'-bipyridine)(methyl)platinum(II) | 162477-74-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: chloro(4,4'-di-tert-butyl-2,2'-bipyridine)(methyl)platinum(II)
• 英文别名: [PtClMe(4,4'-di-tert-butyl-2,2'-bipyridyl)]；PtCl(methyl)(4,4'-di-tert-butyl-2,2'-bipyridyl)；[Pt(II)ClMe(4,4'-di-tert-butyl-6,6'-bipyridine)]；[PtClMe(4,4'-di-tert-butyl-2,2'-bipyridine)]；4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine;carbanide;chloroplatinum(1+)
• CAS: 162477-74-9
• 化学式: C₁₉H₂₇ClN₂Pt
• 分子量: 513.97
• InChiKey: HPVSAAATIXTSDU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 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：

  chloro(4,4'-di-tert-butyl-2,2'-bipyridine)(methyl)platinum(II) 、 氯 以 二氯甲烷 为溶剂， 以99%的产率得到mer-[PtCl3Me(4,4'-di-tert-butyl-2,2'-bipyridine)]
  参考文献：
  名称：

  甲基（氢）铂（IV）配合物：第一个（μ-氢）二铂（IV）配合物的X射线结构

  摘要：

  复杂FAC - [PTME 3（SO 3 CF 3）（BU 2联吡啶）]（1）（BU 2联吡啶= 4,4'-二-叔丁基-2,2'-联吡啶）反应用NaBH 4至得到[Pt 2（μ-H）Me 6（bu 2 bpy）2 ] SO 3 CF 3（2），这是（μ-氢）双铂（IV）配合物的第一个实例。根据1 H和195的微量分析对复合物2进行了充分表征Pt NMR光谱和X射线晶体学数据。1与大量NaBH 4的反应导致形成2和fac- [PtHMe 3（bu 2 bpy）]（3）的平衡混合物。配合物3在溶液中通过1 H NMR光谱表征，但由于易于还原为2而无法以纯净形式分离。配合物2和3均不具有易于解离的配体，在热稳定性方面对甲烷的还原消除作用（在溶液中以及在配合物2的情况下），并处于固态）和Pt（D）CH 3基团之间的同位素交换，因此为两个反应必须从五坐标中间发生的理论提供了有力的支持。配合物2与HX（HX

  DOI：

  10.1021/om960975l
• 作为产物：
  描述：

  [Pt(CH2SiMe3)2(4,4'-di-tert-butyl-2,2'-bipyridine)] 以 二氯甲烷-D2 为溶剂， 生成 chloro(4,4'-di-tert-butyl-2,2'-bipyridine)(methyl)platinum(II)
  参考文献：
  名称：

  四甲基硅烷中Si-C或C-H键的活化：(三甲基甲硅烷基）甲基-白金键质子分解的证据

  摘要：

  [Pt（CH 2 SiMe 3）2（NN）]（NN = 4,4'-二叔丁基-2,2'-联吡啶）和[Pt（ CH 2 SiMe 3）（NNC）]（NNC = C 6 H 4 -2-CH N-反-C 6 H 10 -2-N建议通过在铂上质子化产生CHPh），得到16电子的氢化铂（IV）中间体，然后快速，一致地重排以生成甲基（三甲基甲硅烷基）铂（IV）复杂的中间体，或进行还原偶联以形成四甲基硅烷（TMS） ）。直接表征（PtBrMe 2（SiMe 3）（NN））等（三甲基硅烷基）铂（IV）复杂中间体证明了三甲基硅烷基团从碳到阳离子铂中心的α迁移很容易，这表明亲电性铂（II）络合物的Si-C键活化可能是CH活化的替代方法。

  DOI：

  10.1021/om0400088

文献信息

• Synthesis and Characterization of Group 14−Platinum(IV) Complexes
  作者：Christopher J. Levy、Jagadese J. Vittal、Richard J. Puddephatt

  DOI：10.1021/om950493u

  日期：1996.4.16

  [PtMe2(diimine)] complexes give facile trans oxidative addition of the E−X bond (E = Si, X = Br, I; E = Ge, Sn, X = Cl, Br, I). The oxidative additions occur more readily for MenEX4-n in the sequences X = I > Br > Cl and E = Sn > Ge > Si. The first stable silylplatinum(IV) complexes have been prepared in this way, and the X-ray crystal structure of [PtIMe2(Me3Si)(bpy)] shows an exceptionally long Pt−I bond length

  第14组化合物Me n EX 4- n（E = Si，Ge，Sn; X = Cl，Br，I）与富电子的[PtMe 2（diimine ）]配合物的反应可轻松实现E-的反氧化加成X键（E = Si，X = Br，I; E = Ge，Sn，X = Cl，Br，I）。对于Me n EX 4- n而言，以X = I> Br> Cl和E = Sn> Ge> Si的顺序更容易发生氧化加成。以这种方式制备了第一个稳定的甲硅烷基铂（IV）配合物，[PtIMe 2（Me 3 Si）（bpy）]的X射线晶体结构显示了异常长的Pt-I键长（2.963（1）Å ）与高反三甲基甲硅烷基的影响。1 H NMR研究表明，涉及锗和锡试剂的氧化加成反应易于逆转。几种铂（IV）-锡配合物具有掺入晶格中的第二分子锡试剂。[PtIMe 2（Me 3 Sn）（bpy- t bu 2）] 2 ·Me 3 SnI·CH 2 Cl 2的
• Thermal Decomposition of Platinum(IV)−Silicon, −Germanium, and −Tin Complexes
  作者：Christopher J. Levy、Richard J. Puddephatt

  DOI：10.1021/om970204x

  日期：1997.9.1

  The thermal decomposition of a number of complexes of the type [PtMe2(Me3E)X(diimine)] (E = Si, Ge, Sn; X = Cl, Br, I) has been studied. The thermal stability of complexes, as determined by thermogravimetric analysis (TGA), varies depending on the diimine ligand in the order 2,2‘-bipyridyl (bpy) > 4,4‘-di-tert-butyl-2,2‘-bipyridyl (bpy-tbu2) > N-(2-(dimethylamino)ethyl)pyridine-2-aldimine (paen-me2)

  已经研究了[PtMe 2（Me 3 E）X（二亚胺）]（E = Si，Ge，Sn; X = Cl，Br，I）类型的许多配合物的热分解。配合物的热稳定性，如通过热重分析（TGA）来确定，取决于在顺序二亚胺配2,2'-联二吡啶（BPY）> 4,4'-二-叔丁基-2,2'-联吡啶（bpy- tbu 2）> N-（2-（二甲基氨基）乙基）吡啶-2-醛亚胺（pame-me 2）>（2-亚氨基-正丙基）吡啶（py- n -pr）。稳定性还根据趋势E = Sn≈Ge> Si和X = I> Br> Cl而变化。热分解的产品也已通过确定1还原消除的Me：1 H NMR和分解的三种不同模式是显而易见的3 EX，还原消除的Me 4 E，和Me的α-消除2 E.还原消除之间的竞争Me 3 EX和Me 4 E的比率主要取决于卤化物X，比率Me 3 EX：Me4 ë最高为X = Cl和最低为X = I.还原消除和α-
• Cationic platinum(<scp>II</scp>) complexes: platinum–alkyl bond cleavage by a powerful Lewis acid
  作者：Geoffrey S. Hill、Louis M. Rendina、Richard J. Puddephatt

  DOI：10.1039/dt9960001809

  日期：——

  2′-bipyridine) with AgX (X = SO3CF3 or O2CCF3) gave the complexes [PtMe(SO3CF3)(dbbipy)]1, [Pt(SO3CF3)2(dbbipy)]2 and [Pt(O2CCF3)2(dbbipy)]5. The complexes [PtCl(SO3CF3)(dbbipy)]3 and [PtMe(O2CCF3)(dbbipy)]4 were prepared by the addition of HX to [PtCl2(dbbipy)] or [PtMe2(dbbipy)], respectively. Complex 1 reacted with CO to give the cationic carbonyl complex [PtMe(CO)(dbbipy)][SO3CF3]6a, which reacted with

  [氯铂酸（ME）（dbbipy）]或[氯铂酸的治疗2（dbbipy）]（dbbipy = 4,4'-二-叔与卤化银丁基-2,2'-联吡啶）（X = SO 3 CF 3或O 2 CCF 3）给出络合物[PtMe（SO 3 CF 3）（dbbipy）] 1，[Pt（SO 3 CF 3）2（dbbipy）] 2和[Pt（O 2 CCF 3）2（dbbipy）] 5。[PtCl（SO 3 CF 3）（dbbipy）] 3和[PtMe（O 2 CCF 3）通过向[PtCl 2（dbbipy）]或[PtMe 2（dbbipy）]中添加HX分别制备）（（dbbipy）] 4。配合物1与CO反应生成阳离子羰基配合物[PtMe（CO）（dbbipy）] [SO 3 CF 3 ] 6a，其与NEt 2 H反应生成与相应的氨基甲酸酯配合物[Pt（CONEt 2）Me （（dbbipy）] 7。在通过强路易斯酸B（C
• Fine-Tuning the Basicity of Metal Complexes:  Reversible Oxidative Addition of Se−Se Bonds to Platinum(II) Precursors
  作者：Achille Panunzi、Giuseppina Roviello、Francesco Ruffo

  DOI：10.1021/om020401i

  日期：2002.8.19

  The oxidative addition of diselenides to novel platinum(II) precursors affording octahedral platinum(IV) products was investigated. The properties of the substituents on Pt were finely tailored in order to prompt easy reversibility of the reaction. This allowed the achievement of the first example of equilibrium of oxidative addition of an E−E bond (E = chalcogen) to a Pt(II) precursor. The equilibrium

  研究了二硒化物向新型八面体铂（IV）产物的铂（II）前体的氧化加成反应。精心设计了Pt上取代基的性质，以促进反应的容易可逆性。这实现了将E-E键（E =硫族元素）氧化加成到Pt（II）前体上的平衡的第一个例子。平衡常数可以通过NMR光谱进行评估，并根据空间和电子因素对结果进行了初步合理化。
• Cationic Carbene Complexes of Platinum(IV): Structure of a Secondary Carbene Complex
  作者：Louis M. Rendina、Jagadese J. Vittal、Richard J. Puddephatt

  DOI：10.1021/om00002a058

  日期：1995.2

  Treatment of the organoplatinum(II) precursors [PtMeCl((t)bu(2)bpy)] ((t)bu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) and [PtMe(2)((t)bu(2)bpy)] with chloroiminium (Vilsmeier) salts affords the novel cationic platinum(IV)-carbene complexes [PtCl(2)Me(CHNMe(2))((t)bu(2)bpy)]Cl (1), [PtCl2-Me(CClNMe(2))((t)bu(2)bpy)]Cl (2), [PtClMe(2)(CHNMe(2))((t)bu(2)bpy)]Cl (3), and [PtClM(2)(CClNMe(2))((t)bu(2)bpy)]Cl (4) in good yield. For 1 and 2, the carbene moiety is located trans to one of the chloro ligands, whereas in 3 and 4 it is found trans to the N-donor. The complexes show good stability toward air and moisture, but 1 and 2 are thermally unstable and decompose to [PtCl2((t)bu(2)bpy)] after a few days at room temperature. Complex 4 can also be prepared as a mixture of two geometrical isomers which do not interconvert; it is proposed that the isomers are formed by two independent pathways. The major (4a) and minor (4b) isomers are formed by cis- and trans-oxidative addition, respectively, of [Cl2C=NMe(2)]Cl to [PtMe(2)((t)bu(2)bpy)], and likely mechanisms are discussed. Crystals of 1 are monoclinic, space group P2(1)/c, with a = 11.064(1) Angstrom, b = 21.310(2) Angstrom, c = 12.277(3) Angstrom, beta = 91.20(2)degrees, Z = 4, and R = 0.0718. The structure of 1 consists of discrete [PtCl(2)Me(CHNMe(2))((t)bu(2)bpy)](+) cations and chloride anions, with one CH2Cl2 molecule of crystallization per complex ion. The carbene ligand occupies a position trans to one of the chloro ligands, and the Pt-(Carbene) bond length (1.99(2) Angstrom) is significantly shorter than the Pt-Me distance (2.13(2) Angstrom). The C-N bond length of 1.31(2) Angstrom is indicative of substantial p(pi)-p(pi) bonding. Reaction of nucleophiles with 3 leads to rapid reductive elimination to give an iminium salt [H(X)C = NMe(2)]Cl (X = nucleophile) and [PtMe(2)((t)bu(2)bpy)]. This work demonstrates the versatility of chloroiminium salts in the preparation of aminocarbene complexes of metals in high oxidation states.