chloro[glyoxal-bis((2-α-triisopropylsiloxymethyl)-6-methylphenyl)diimine]methylplatinum(II) | 239127-87-8

• 英文名称: chloro[glyoxal-bis((2-α-triisopropylsiloxymethyl)-6-methylphenyl)diimine]methylplatinum(II)
• CAS: 239127-87-8
• 化学式: C₃₇H₆₃ClN₂O₂PtSi₂
• 分子量: 854.623
• InChiKey: VHAWUHWXDUSAMI-BUAHPEKYSA-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：
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• sp3杂化的碳原子比例：
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• 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：

  乙烯 、 chloro[glyoxal-bis((2-α-triisopropylsiloxymethyl)-6-methylphenyl)diimine]methylplatinum(II) 、 silver tetrafluoroborate 以 二氯甲烷 为溶剂， 以75%的产率得到ethylene[glyoxal-bis((2-α-triisopropylsiloxymethyl)-6-methylphenyl)diimine]methylplatinum(II) tetrafluoroborate
  参考文献：
  名称：

  Cationic Unsymmetrical 1,4-Diazabutadiene Complexes of Platinum(II)

  摘要：

  The synthesis of the silyl-protected 1,4-diazabutadiene ligands glyoxal-bis((2-alpha-triisopropylsiloxymethyl)-6-methylphenyl)diimine (TIPS-6-MPD) and glyoxal-bis((2-alpha-triisopropylsiloxymethyl)-4-methylphenyl)diimine (TIPS-4-MPD) and their subsequent reactions with trans-Pt(SMe2)(2)(Me)Cl to generate the corresponding complexes (TIPS-6-MPD)Pt(Me)Cl (1a) and (TIPS-4-MPD)Pt(Me)Cl (Ib) are described. Cationic complexes of the type [(N,N-chelate)Pt(Me)(L)]BF4 (where L = solvent/olefin and N,N-chelate = TIPS-6-MPD and TIPS-4-MPD) are generated by the reaction of chloro methyl complexes la and Ib with AgBF4 in the presence of L. Various exchange reactions were examined for [(TIPS-6-MPD)Pt(Me)(NCCH3)]BF4 (2a), in which it was determined that the coordinated solvent reversibly exchanges with acrylonitrile, ethylene, fumaronitrile, cis-pentenenitrile, benzonitrile, dimethyl sulfide, and carbon monoxide to generate the corresponding cationic complexes 3-9, respectively. Kinetics experiments under pseudo-first-order conditions using 10-, 20-, and 30-fold excesses of benzonitrile demonstrate that 2a undergoes ligand exchange via an associative pathway with st bimolecular rate constant k(2) of (3.2 +/- 2.0) x 10(-4) M-1 s(-1). Complex 2a was found to initiate the polymerization of various electron-rich monomers. A detailed analysis of the reaction demonstrates that the initiation is cationic in nature. The molecular structure of TIPS-6-MPD has been determined by a single-crystal X-ray diffraction analysis. The free ligand adopts an s-trans conformation with a planar N=C-C=N backbone.

  DOI：

  10.1021/om000052x
• 作为产物：
  描述：

  trans-[PtCl(Me)(SMe2)2] 、 glyoxal-bis((2-α-triisopropylsiloxymethyl)-6-methylphenyl)diimine 以 二氯甲烷 为溶剂， 以91%的产率得到chloro[glyoxal-bis((2-α-triisopropylsiloxymethyl)-6-methylphenyl)diimine]methylplatinum(II)
  参考文献：
  名称：

  Cationic Unsymmetrical 1,4-Diazabutadiene Complexes of Platinum(II)

  摘要：

  The synthesis of the silyl-protected 1,4-diazabutadiene ligands glyoxal-bis((2-alpha-triisopropylsiloxymethyl)-6-methylphenyl)diimine (TIPS-6-MPD) and glyoxal-bis((2-alpha-triisopropylsiloxymethyl)-4-methylphenyl)diimine (TIPS-4-MPD) and their subsequent reactions with trans-Pt(SMe2)(2)(Me)Cl to generate the corresponding complexes (TIPS-6-MPD)Pt(Me)Cl (1a) and (TIPS-4-MPD)Pt(Me)Cl (Ib) are described. Cationic complexes of the type [(N,N-chelate)Pt(Me)(L)]BF4 (where L = solvent/olefin and N,N-chelate = TIPS-6-MPD and TIPS-4-MPD) are generated by the reaction of chloro methyl complexes la and Ib with AgBF4 in the presence of L. Various exchange reactions were examined for [(TIPS-6-MPD)Pt(Me)(NCCH3)]BF4 (2a), in which it was determined that the coordinated solvent reversibly exchanges with acrylonitrile, ethylene, fumaronitrile, cis-pentenenitrile, benzonitrile, dimethyl sulfide, and carbon monoxide to generate the corresponding cationic complexes 3-9, respectively. Kinetics experiments under pseudo-first-order conditions using 10-, 20-, and 30-fold excesses of benzonitrile demonstrate that 2a undergoes ligand exchange via an associative pathway with st bimolecular rate constant k(2) of (3.2 +/- 2.0) x 10(-4) M-1 s(-1). Complex 2a was found to initiate the polymerization of various electron-rich monomers. A detailed analysis of the reaction demonstrates that the initiation is cationic in nature. The molecular structure of TIPS-6-MPD has been determined by a single-crystal X-ray diffraction analysis. The free ligand adopts an s-trans conformation with a planar N=C-C=N backbone.

  DOI：

  10.1021/om000052x