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首页> 外文期刊>Journal of Inorganic Biochemistry: An Interdisciplinary Journal >Half-sandwich rhodium(III) transfer hydrogenation catalysts: Reduction of NAD(+) and pyruvate, and antiproliferative activity
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Half-sandwich rhodium(III) transfer hydrogenation catalysts: Reduction of NAD(+) and pyruvate, and antiproliferative activity

机译：半三明治铑（III）转移加氢催化剂：还原NAD（+）和丙酮酸，并具有抗增殖活性

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Organometallic complexes have the potential to behave as catalytic drugs. We investigate here Rh(III) complexes of general formula [(Cp-x)Rh(N,NO(Cl)], where N,N' is ethylenediamine (en), 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen) or N-(2-aminoethyl)-4-(trifluoromethyl)benzenesulfonamide (TfEn), and Cp-x is pentamethylcyclopentadienyl (Cp-xPhPh), 1-phenyl-2,3,4,5-tetramethylcyclopentadienyl (Cp-xPh) or 1-biphenyl-2,3,4,5-tetramethyl cyclopentadienyl (Cp-xPhPh). These complexes can reduce NAD(+) to NADH using formate as a hydride source under biologically-relevant conditions. The catalytic activity decreased in the order of N,N-chelated ligand bpy > phen > en with Cp* as the eta(5)-donor. The en complexes (1-3) became more active with extension to the Cp-X ring, whereas the activity of the phen (7-9) and bpy (4-6) compounds decreased. [Cp*Rh(bpy)Cl](+) (4) showed the highest catalytic activity, with a TOF of 37.4 +/- 2 h(-1). Fast hydrolysis of the chlorido complexes 1-10 was observed by H-1 NMR (<10 min at 310 K). The pK(a)* values for the aqua adducts were determined to be ca. 8-10. Complexes 1-9 also catalysed the reduction of pyruvate to lactate using formate as the hydride donor. The efficiency of the transfer hydrogenation reactions was highly dependent on the nature of the chelating ligand and the Cp-x ring. Competition reactions between NAD(+) and pyruvate for reduction by formate catalysed by 4 showed a preference for reduction of NAD(+). The antiproliferative activity of complex 3 towards A2780 human ovarian cancer cells increased by up to 50% when administered in combination with nontoxic doses of formate, suggesting that transfer hydrogenation can induce reductive stress in cancer cells. (C) 2015 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
机译：有机金属络合物具有充当催化药物的潜力。我们在这里研究通式[[Cp-x] Rh（N，NO（Cl）]的Rh（III）配合物，其中N，N'是乙二胺（en），2,2'-联吡啶（bpy），1 10-菲咯啉（phen）或N-（2-氨基乙基）-4-（三氟甲基）苯磺酰胺（TfEn），Cp-x是五甲基环戊二烯基（Cp-xPhPh），1-苯基-2,3,4,5-四甲基环戊二烯基（Cp-xPh）或1-biphenyl-2,3,4,5-四甲基环戊二烯基（Cp-xPhPh）。在生物相关条件下，使用甲酸作为氢化物源，这些络合物可以将NAD（+）还原为NADH。活性按N，N-螯合配体bpy> phen> en的顺序降低，Cp *为eta（5）-给体。en配合物（1-3）随着扩展到Cp-X环而变得更有活性，而phen（7-9）和bpy（4-6）化合物的活性降低[Cp * Rh（bpy）Cl]（+）（4）表现出最高的催化活性，TOF为37.4 +/- 2 h（-1）。通过H-1 NMR（在310 K下<10分钟）观察到了氯配合物1-10的快速水解，水合加合物的pK（a）*值确定为。 8-10。配合物1-9也催化使用甲酸盐作为氢化物供体将丙酮酸还原为乳酸盐。转移氢化反应的效率高度依赖于螯合配体和Cp-x环的性质。 NAD（+）与丙酮酸之间的竞争反应（被4催化）被甲酸还原显示出对NAD（+）还原的偏好。当与无毒剂量的甲酸盐组合使用时，复合物3对A2780人卵巢癌细胞的抗增殖活性提高了50％，这表明转移氢化可以诱导癌细胞中的还原性应激。 （C）2015作者。由Elsevier Inc.发行。这是CC BY许可（http://creativecommons.org/licenses/by/4.0/）下的开放访问文章。

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