Novel dinuclear platinum(II) complexes containing mixed nitrogen-sulfur donor ligands.
Novel dinuclear platinum(II) complexes containing mixed nitrogen-sulfur donor ligands.
复制标题
含有混合氮硫供体配体的新型双核铂(II)配合物
DOI：
10.1021/ic2018902
复制
发表时间：
2011
影响因子：
4.6
通讯作者：
van Eldik
中科院分区：
文献类型：
--
作者：
Hochreuther;Puchta;van Eldik
合成了一系列新型的双核铂（II）配合物，其中两个铂中心由一个可变长度的脂肪链连接，构成一个氮硫混合双齿螯合体系。选择双齿螯合配体来稳定络合物以防止分解。合成的四种配合物，即[Pt 2（S1，S4-双（2-吡啶基甲基）-1，4-丁二硫醚）（OH 2）4]4+（4 NSpy），[Pt 2（S1，S6-双（2-吡啶基甲基）-1，6-己二硫醚）（OH 2）4]4+（6 NSpy），[Pt 2（S1，S8-双（2-吡啶甲基）-1，8-辛二硫醚）（OH_2）_4]~（4+）（8 NSpy）和[Pt_2（S1，S10-双（2-吡啶甲基）-1，10-癸二硫醚）（OH_2）_4]~（4+）（10 NSpy）。这个系统是特别感兴趣的，因为只有很少有人知道双核铂配合物的取代行为，包含一个双齿螯合物，形成部分的脂肪族桥接配体。此外，配体以及双核配合物进行了检查，在其细胞毒活性方面，和10 NSpycomplex被发现是积极的。进行分光光度酸碱滴定以确定所有配位水分子的pKa值。利用停流技术和紫外-可见光谱研究了硫脲取代配位水反应在准一级反应条件下与亲核试剂浓度、温度和压力的关系。将双核配合物的结果与相应的单核参考配合物[Pt（methylthiomethylpyridine）（OH 2）2]2+（Pt（mtp））的结果进行比较，通过该结果可以研究桥接配合物的增加的脂肪链长度的影响。结果表明，两个铂中心之间存在明显的相互作用，并且随着金属中心之间链长的增加，这种相互作用逐渐减弱。此外，还比较了N，S-体系与本课题组以前研究的相应双核N，N-体系的异同。此外，量子化学计算进行支持的解释和讨论的实验数据。
A series of novel dinuclear platinum(II) complexes were synthesized containing a mixed nitrogen–sulfur donor bidentate chelate system in which the two platinum centers are connected by an aliphatic chain of variable length. The bidentate chelating ligands were selected to stabilize the complex toward decomposition. The pKavalues and reactivity of the four synthesized complexes, namely, [Pt2(S1,S4-bis(2-pyridylmethyl)-1,4-butanedithioether)(OH2)4]4+(4NSpy), [Pt2(S1,S6-bis(2-pyridylmethyl)-1,6-hexanedithioether)(OH2)4]4+(6NSpy), [Pt2(S1,S8-bis(2-pyridylmethyl)-1,8-octanedithioether)(OH2)4]4+(8NSpy), and [Pt2(S1,S10-bis(2-pyridylmethyl)-1,10-decanedithioether)(OH2)4]4+(10NSpy), were investigated. This system is of special interest because only little is known about the substitution behavior of dinuclear platinum complexes that contain a bidentate chelate that forms part of the aliphatic bridging ligand. Moreover, the ligands as well as the dinuclear complexes were examined in terms of their cytotoxic activity, and the10NSpycomplex was found to be active. Spectrophotometric acid–base titrations were performed to determine the pKavalues of all the coordinated water molecules. The substitution of coordinated water by thiourea was studied under pseudo-first-order conditions as a function of nucleophile concentration, temperature, and pressure, using stopped-flow techniques and UV–vis spectroscopy. The results for the dinuclear complexes were compared to those for the corresponding mononuclear reference complex [Pt(methylthiomethylpyridine)(OH2)2]2+(Pt(mtp)), by which the effect of the increasing aliphatic chain length of the bridged complexes could be investigated. The results indicate that there is a clear interaction between the two platinum centers, which becomes weaker as the chain length between the metal centers increases. Furthermore, differences and similarities of the N,S-system were compared to the corresponding dinuclear N,N-system studied previously in our group. In addition, quantum chemical calculations were performed to support the interpretation and discussion of the experimental data.
登录
查看更多内容
DOI：
--
发表时间：
1999
期刊：
影响因子：
--
作者：
G. Stochel;R. Eldik
通讯作者：
R. Eldik
DOI：
--
发表时间：
1990
期刊：
影响因子：
--
作者：
Y. Qu;N. Farrell
通讯作者：
N. Farrell
水解会引发反式二胺铂 (II) 抗癌复合物的氧化。
影响因子：
--
作者：
Ana M. Pizarro;Vivienne P. Munk;C. Navarro‐Ranninger;P. Sadler
通讯作者：
P. Sadler
DOI：
--
发表时间：
1978
期刊：
影响因子：
--
作者：
R. Wilkinson;P. Cox;Michael G. K. Jones;K. Harrap
通讯作者：
K. Harrap
氨/胺铂(II)和(IV)配合物的合成和抗肿瘤活性。
影响因子：
3.9
作者：
Khokhar,AR;Deng,Y;al-Baker,S;Yoshida,M;Siddik,ZH
通讯作者：
Siddik,ZH