trans-[PtCl2(NCNC5H10)(-N=C(NC5H10)ON(C6H4Cl-p)CPh2-)] | 1354485-50-9

• 英文名称: trans-[PtCl2(NCNC5H10)(-N=C(NC5H10)ON(C6H4Cl-p)CPh2-)]
• CAS: 1354485-50-9
• 化学式: C₃₁H₃₄Cl₃N₅OPt
• 分子量: 794.083
• InChiKey: VKSTVKWENXZKKG-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  trans-[PtCl2(NCN(CH2)5)2] 、 Ph2C=N(O)C6H4Cl-p 以 氯仿 为溶剂， 以81%的产率得到trans-[PtCl2(NCNC5H10)(-N=C(NC5H10)ON(C6H4Cl-p)CPh2-)]
  参考文献：
  名称：

  Facile and Reversible 1,3-Dipolar Cycloaddition of Aryl Ketonitrones to Platinum(II)-Bound Nitriles: Synthetic, Structural, and Theoretical Studies

  摘要：

  The reaction between trans-[PtCl2(NCR)(2)] (R = Et 1, NMe2 2, NEt2 3, NC5H10 4) and the acyclic triaryl ketonitrones Ph2C=N(O)C6H4R'-p (R' = H 5, Me 6, Cl 7, OMe 8) proceeds as a facile and consecutive two-step intermolecular cycloaddition to give the mono-cycloaddition products trans-[PtCl2(NCR){N-a= C(R)ON(C6H4R'-p)(CPh2)-Ph-b}]((a-b)) (R/R' = Et/H 9, Et/Me 10, Et/Cl 11, Et/OMe 12, NMe2/H 13, NMe2/Me 14, NMe2/Cl 15, NMe2/OMe 16, NEt2/H 17, NEt2/Me 18, NEt2/Cl 19, NEt2/OMe 20, NC5H10/H 21, NC5H10/Me 22, NC5H10/Cl 23, NC5H10-/OMe 24) and then the bis-2,3-dihydro-1,2,4-oxadiazole complexes trans[PtC12{N-a=C(R)ON(C6H4R'-p)(CPh2)-Ph-b}(2)]((a-b)) (R/R' = Et/H 25, Et/Me 26, Et/Cl 27, Et/OMe 28, NMe2/H 29, NMe2/Me 30, NMe2/Cl 31, NMe2/OMe 32, NEt2/H 33, NEt2/Me 34, NEt2/Cl 35, NEt2/OMe 36, NC5H10/H 37, NC5H10/Me 38, NC5H10/Cl 39, NC5H10/OMe 40). The ketonitrones Ph2C=N(O)C6H4R'-p were found to be unexpectedly much more reactive toward the platinum(II)-bound nitriles than the related aldonitrones p-R ''' C6H4CH=N(O)R ''(R '' = Me, Ph; R ''' = H, Me), and the difference in the reactivity in 1,3-dipolar cycloaddition (DCA) of the keto- and aldonitrones was interpreted by theoretical calculations and was explained in terms of the orbital arguments as a result of the increase of the HOMOnitrone energy from aldo- to ketonitrones. The first example of the reversibility in metal-mediated DCA of nitrones to nitriles was observed, and this phenomenon, as follows from the performed theoretical study, is justified by the thermodynamic instability of the Pt-II-bound 3,3-diary1-2,3-dihydro-1,2,4-oxadiazoles. Metal-free C-5-dipheny1-2,3-dihydro-1,2,4-oxadiazoles 42 and 43 were liberated from corresponding (oxadiazole)(2)Pt-II complexes 26 and 30 by treatment with excess NaCN, and these heterocycles were characterized by high-resolution ESI+-MS and H-1 and C-13{H-1} NMR spectroscopies.

  DOI：

  10.1021/om201026n