Cullinane Carleen, Deacon Glen B, Drago Penny R, Erven Anja P, Junk Peter C, Luu Jenny, Meyer Gerd, Schmitz Simon, Ott Ingo, Schur Julia, Webster Lorraine K, Klein Axel
Peter MacCallum Cancer Center, 305 Grattan Street, Melbourne Vic 3000, Australia and Sir Peter MacCallum Department of Oncology, University of Melbourne, Parkville, Melbourne Vic 3052, Australia.
Dalton Trans. 2018 Feb 6;47(6):1918-1932. doi: 10.1039/c7dt04615d.
New organometallic complexes [M(dppe)(R)] {where M = Pt or Pd, dppe = 1,2-bis(diphenylphosphano)ethane, and R = CFH-x (x = 6,5,4), CFH-3,5, CFH-5,6, CFH-3,6, CF(OMe)-4, and CF(cyclo-CHN)-4, the numbers x refer to the positions of the protons in the polyfluoroaryl ligands} were synthesised either through transmetalation from the dichlorido complexes [M(dppe)Cl] or through ligand exchange using [M(diene)Cl] precursor complexes with diene = 1,5-cyclooctadiene (cod) or 1,5-hexadiene (hex). Alternatively, [M(dppX)Cl(R)] complexes with dppX = dppm (1,1-bis(diphenylphosphano)methane), dppe, dppp (1,3-bis(diphenylphosphano)propane), and dppb (1,4-bis(diphenylphosphano)butane) were prepared in decarboxylation reactions from thallium(i) carboxylates Tl(OCR). The different preparative methods were compared in terms of yield and purity. Structural and spectroscopic data are reported for the new dppX- and diene-M(R) complexes. Antiproliferative activity was investigated for these new complexes against the HT-29 (colon carcinoma) and MCF-7 (breast adenocarcinoma) cell lines, and the active compounds of this first series together with organometallic dppX or hex Pt or Pd complexes were then included in cell tests using L1210 (leukaemia cells) and the cisplatin-resistant L1210/DDP cell line. Remarkably, promising antiproliferative results were found for a few Pt and Pd complexes, while structurally closely related compounds were essentially nontoxic.
合成了新型有机金属配合物[M(dppe)(R)]（其中M = Pt或Pd，dppe = 1,2 - 双（二苯基膦基）乙烷，R = CFH - x（x = 6,5,4）、CFH - 3,5、CFH - 5,6、CFH - 3,6、CF(OMe) - 4和CF(环 - CHN) - 4，数字x表示多氟芳基配体中质子的位置），其合成方法要么是通过二氯配合物[M(dppe)Cl]进行金属转移，要么是使用二烯 = 1,5 - 环辛二烯（cod）或1,5 - 己二烯（hex）的[M(二烯)Cl]前体配合物进行配体交换。另外，通过铊（Ⅰ）羧酸盐Tl(OCR)的脱羧反应制备了dppX = dppm（1,1 - 双（二苯基膦基）甲烷）、dppe、dppp（1,3 - 双（二苯基膦基）丙烷）和dppb（1,4 - 双（二苯基膦基）丁烷）的[M(dppX)Cl(R)]配合物。从产率和纯度方面比较了不同的制备方法。报道了新型dppX - 和二烯 - M(R)配合物的结构和光谱数据。研究了这些新型配合物对HT - 29（结肠癌细胞）和MCF - 7（乳腺腺癌细胞）细胞系的抗增殖活性，然后将该第一系列的活性化合物与有机金属dppX或hex Pt或Pd配合物一起用于L1210（白血病细胞）和顺铂耐药的L1210/DDP细胞系的细胞测试。值得注意的是，发现一些Pt和Pd配合物有良好的抗增殖结果，而结构密切相关的化合物基本无毒。
