Cini Renzo, Defazio Sandra, Tamasi Gabriella, Casolaro Mario, Messori Luigi, Casini Angela, Morpurgo Margherita, Hursthouse Michael
Department of Chemical and Biosystem Sciences and Technologies, University of Siena, Via Aldo Moro 2, I-53100 Siena, Italy.
Inorg Chem. 2007 Jan 8;46(1):79-92. doi: 10.1021/ic060755s.
The reaction of [Ru2(CO)6Cl4], 1, with excess THZ (1,3-thiazole) in absolute ethanol at 55 degrees C produces fac-[Ru(CO)3Cl2(THZ)], 2, in high yield. [Ru(CO)2Cl2(THZ)2], 3, is formed at higher temperature (ca 70 degrees C) and higher concentration of THZ. The X-ray structures of the new compounds have been determined, and density functional studies performed at the hybrid B3LYP/(Lanl2DZ, Ru; 6-311+G**, CHClNOS) level allowed the estimation of the structures of several conformers as well as that of their relative total electronic energies. Compound 2 is soluble (slowly) in aqueous media, where it reacts with the transport proteins bovine serum albumin (BSA) and human apotransferrin (HTF), and at a lower extent with calf thymus DNA (CT-DNA) and with guanosine-5'-monophosphate (GMP). The complex molecule is adsorbed by certain synthetic acryloyl polymers that have terminal carboxylate functions and is embedded in silica gels when these latter are prepared in the presence of a solution of 2. Ruthenium species are slowly released from the loaded gels into physiological solutions at pH 7.4. The reactivity of 2 with biomolecules and synthetic hydrogels makes it a compound of interest for anticancer and antimetastases tests.
[Ru2(CO)6Cl4]（1）与过量的1,3 - 噻唑（THZ）在55摄氏度的无水乙醇中反应，高产率地生成面式 - [Ru(CO)3Cl2(THZ)]（2）。在较高温度（约70摄氏度）和较高浓度的THZ条件下会形成[Ru(CO)2Cl2(THZ)2]（3）。已测定了这些新化合物的X射线结构，并在杂化B3LYP/(Lanl2DZ, Ru; 6 - 311 + G**, CHClNOS)水平上进行了密度泛函研究，从而能够估算几种构象异构体的结构及其相对总电子能量。化合物2可（缓慢）溶于水介质，在其中它会与转运蛋白牛血清白蛋白（BSA）和人脱铁转铁蛋白（HTF）发生反应，与小牛胸腺DNA（CT - DNA）和鸟苷 - 5'- 单磷酸（GMP）的反应程度较低。该复合分子会被某些具有末端羧酸盐功能的合成丙烯酰聚合物吸附，并且当在2的溶液存在下制备硅胶时会嵌入其中。钌物种会从负载的凝胶中缓慢释放到pH值为7.4的生理溶液中。2与生物分子和合成水凝胶的反应活性使其成为用于抗癌和抗转移测试的一种有意义的化合物。
