chloro(1,2-ethanediamine-κ(2)N,N')(1,1,3,3-tetramethylthiourea-κS)platinum(II) nitrate | 202073-18-5

• 英文名称: chloro(1,2-ethanediamine-κ(2)N,N')(1,1,3,3-tetramethylthiourea-κS)platinum(II) nitrate
• CAS: 202073-18-5
• 化学式: C₇H₂₀ClN₄PtS*NO₃
• 分子量: 484.867
• InChiKey: ZHEDZFFWLNBPMN-UHFFFAOYSA-M

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

• 作为反应物：
  描述：

  chloro(1,2-ethanediamine-κ(2)N,N')(1,1,3,3-tetramethylthiourea-κS)platinum(II) nitrate 、 guanosine 5'-monophosphate disodium 以 重水 为溶剂， 生成
  参考文献：
  名称：

  Modification of Platinum(II) Antitumor Complexes with Sulfur Ligands. 2. Reactivity and Nucleotide Binding Properties of Cationic Complexes of the Types [PtCl(diamine)(L)]NO₃ and [{PtCl(diamine)}₂(L-L)](NO₃)₂ (L = Monofunctional Thiourea Derivative; L-L = Bifunctional Thiourea Derivative) in Relation to Their Cytotoxicity

  摘要：

  The reactions of [PtCl(en)(tmtu)]NO3 (1) and [PtCl(dach)(tmtu)]NO3 (2) (en = 1,2-ethanediamine, dach = racemic trans-1,2-cyclohexanediamine, tmtu = 1,1,3,3-tetramethylthiourea) and [{Pt(en)Cl}(2){mu-C2H4(NMeCSNMe2)(2)-S,S}](NO3)(2) (3) and [{Pt(en)Cl}(2){mu-C6H12(NMeCSNMe2)(2-)S,S'}](NO3)(2) . 0.5EtOH (4) with 5'-GMP and r(GpG) and their chemistry in aqueous solution have been investigated by H-1 and Pt-195 NMR spectroscopy. 1 and 2 only form the monofunctional adducts [Pt(en)(5'-GMP-N7)(tmtu)] (I) and [Pt(dach)(5'-GMP-NT)(tmtu)] (II), irrespective of an excess of free nucleotide. Pt-195 NMR chemical shifts of -3003 and -2982 ppm, respectively, confirm a [N3S] mixed-donor environment of platinum. The bulky tmtu ligand in 1 and 2 decreases the rate of hydrolysis of the Pt-Cl bond and the rate of nucleotide binding compared to analogous reactions for cisplatin and structural analogues. The dinuclear complexes 3 and 4 exhibit an unusual rapid intramolecular disproportionation in solution (t(1/2) = 2.5 and 12 h, respectively) which yields [PtCl2(en)] and [Pt(en)(L-L)](2+) (L-L = chelating bifunctional thiourea derivative; delta(Pt) -3454 with L-L = C2H4(NMeCSNMe2)(2)). Accordingly, 3 forms the mononuclear adducts [Pt(en)(5'-GMP-N7)(2)] (III) and [Pt(en){r(GpG)-N7(1),N7(2)}] (IV). Due to the considerably slower rate of decomposition, I gives both the dinuclear adduct [{Pt(en)}(2){mu-C6H12(NMeCSNMe2)(2)}{mu-r(GpG)-N7(1),N7(2)}] (V) (70%) and IV (30%). The 5' sugar residue of r(GpG) in IV exhibits an N-type conformation, as commonly observed in bifunctional adducts that are formed between Pt(II) antitumor complexes and dinucleotides. The absence of this structural feature in V supports the formation of a conformationally less restricted macrochelate. Cytotoxicity data for 1-4 in L1210 leukemia are in accordance with the nucleotide-binding properties of 1 and 2 and the aqueous solution chemistry of the dinuclear compounds 3 and 4. The results indicate that structurally modified thiourea ligands may be interesting for their use as alternative, strongly coordinating carrier groups in platinum(II) antitumor complexes.

  DOI：

  10.1021/ic970421q
• 作为产物：
  描述：

  乙二胺氯化铂(II) 、 四甲基硫脲 、 silver nitrate 以 N,N-二甲基甲酰胺 为溶剂， 以59%的产率得到chloro(1,2-ethanediamine-κ(2)N,N')(1,1,3,3-tetramethylthiourea-κS)platinum(II) nitrate
  参考文献：
  名称：

  Modification of Platinum(II) Antitumor Complexes with Sulfur Ligands. 1. Synthesis, Structure, and Spectroscopic Properties of Cationic Complexes of the Types [PtCl(diamine)(L)]NO₃ and [{PtCl(diamine)}₂(L-L)](NO₃)₂ (L = Monofunctional Thiourea Derivative; L-L = Bifunctional Thiourea Derivative)

  摘要：

  A new class of mono-and dinuclear platinum(II) complexes is described that derives from the cisplatin analogues (Pt(en)Cl-2] and [Pt(dach)Cl-2] (en = 1,2-ethanediamine, dach = racemic trans-1,2-cyclohexanediamine). The selective substitution of one chloro ligand in these species by 1,1,3,3-tetramethylthiourea (tmtu), which requires abstraction of chloride with silver salt in DMF, gives [PtCl(en)(tmtu)]NO3 (1) and [PtCl(dach)(tmtu)]NO3 (2). Similarly, reactions employing the novel bifunctional thiourea derivatives C2H4(NMeCSNMe2)(2) (3) and C6H12-(NMeCSNMe2)(2) (4) yield the dinuclear complexes [{Pt(en)Cl}(2)(mu-3-S,S')](NO3)(2) (5) and [{Pt(en)Cl}(2)(mu-4-S,S')]-(NO3)(2) . 0.5EtOH (6), respectively. The compounds were characterized by H-1, C-13, and Pt-195 Nh IR spectroscopy, elemental analyses, and IR data, Pt-195 chemical shifts in the -2895 to -2929 ppm region confirm the mixed-donor [PtN2ClS] coordination for 1, 2, 5, and 6 and thiourea-S coordination in all cases, The single-crystal X-ray structures of 2-4 have been determined. 2: monoclinic, space group P2(1)/n, a = 10.804 Angstrom, b = 16.221 Angstrom, c = 21.789 Angstrom, beta = 102.16(1)degrees, Z = 8. 3: monoclinic, space group P2(1)/n, a = 12.787(2) Angstrom, b = 6.250(1) Angstrom, c = 17.777(3) Angstrom, beta = 98.21(1)degrees, Z = 4. 4: monoclinic, space group P2(1)/n, a = 11.097(3) Angstrom, b = 13.717 Angstrom, c = 11.925 Angstrom, beta = 97.61(2)degrees, Z = 4. The Pt-S distance in 2 (2.285(2) Angstrom, mean) is in accordance with the magnitude of shielding found for the Pt-195 core and suggests weak pi-acceptor properties of tmtu. The bifunctional thiourea derivatives 3 and 4 adopt highly elongated conformations in the solid state where the sulfur atoms and the n-(CH2)(n), (n = 2, 6) linkers are Z-oriented. Force field calculations on 3 and 1 imply that the Z-form should be the prefer-red conformer for the thiourea groups in solution, H-1 NMR spectra indicate a dynamic equilibrium of different rotamers due to low barriers of rotation within the thiourea moieties in free and coordinated 3 and 4. It is suggested that the steric and electronic effects of the peralkylated thiourea derivatives in 1, 2, 5, and 6 may modulate the affinity of the complexes for biomolecules.

  DOI：

  10.1021/ic970420y