000190920 001__ 190920
000190920 005__ 20181203023333.0
000190920 0247_ $$2doi$$a10.1039/c3dt51991k
000190920 022__ $$a1477-9226
000190920 02470 $$2ISI$$a000325944000027
000190920 037__ $$aARTICLE
000190920 245__ $$aSynthesis, molecular structure, computational study and in vitro anticancer activity of dinuclear thiolato-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) complexes
000190920 260__ $$bRoyal Society of Chemistry$$c2013$$aCambridge
000190920 269__ $$a2013
000190920 300__ $$a7
000190920 336__ $$aJournal Articles
000190920 520__ $$aNeutral dinuclear dithiolato-bridged pentamethylcyclopentadienyl Rh(III) complexes of the type (C5Me5)(2)Rh-2(mu-SR)(2)Cl-2 (R = CH2Ph, 1; R = CH2CH2Ph, 2) and cationic dinuclear trithiolato-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) complexes of the type [(C5Me5)(2)M-2(mu-SR)(3)](+) (M = Rh, R = CH2Ph, 3; M = Rh, R = CH2CH2Ph, 5; M = Rh, R = CH2C6H4-p-tBu, 7: M = Ir, R = CH2Ph, 4; M = Ir, R = CH2CH2Ph, 6; M = Ir, R = CH2C6H4-p-tBu, 8) have been synthesized from the chloro-bridged pentamethylcyclopentadienyl Rh(III) and Ir(III) dimers (C5Me5)(2)M-2(mu-Cl)(2)Cl-2 by reaction with the corresponding thiol derivative (RSH). Complexes 3-8 were isolated as chloride salts. All complexes were obtained in good yield and were fully characterized by spectroscopic methods. The molecular structures of the neutral complexes (1 and 2) show interesting features: the two rhodium atoms are bridged by two thiolato ligands with no metal-metal bonds and the pentamethylcyclopentadienyl and chlorido ligands are oriented syn to each other, an uncommon conformation for such dinuclear complexes. These structural features were rationalized using DFT calculations. Additionally, the antiproliferative activity of the complexes was evaluated against the cancerous A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) human ovarian cell lines and on the noncancerous HEK293 human embryonic kidney cells. All complexes were found to be active and the cationic iridium complexes 4, 6 and 8 are particularly cytotoxic, with IC50 values in the nanomolar range (IC50 < 0.1 mu M). The catalytic activity of the complexes for the oxidation of glutathione (GSH) to GSSG was evaluated by NMR spectroscopy.
000190920 700__ $$uUniv Neuchatel, Inst Chem, CH-2000 Neuchatel, Switzerland$$aGupta, Gajendra
000190920 700__ $$uUniv Neuchatel, Inst Chem, CH-2000 Neuchatel, Switzerland$$aGarci, Amine
000190920 700__ $$0245493$$g214821$$uEcole Polytech Fed Lausanne, Inst Sci & Ingn Chim, CH-1015 Lausanne, Switzerland$$aMurray, Benjamin S.
000190920 700__ $$0240015$$g149418$$uEcole Polytech Fed Lausanne, Inst Sci & Ingn Chim, CH-1015 Lausanne, Switzerland$$aDyson, Paul J.
000190920 700__ $$uUniv Limoges, Fac Pharm, LCSN EA1069, F-87025 Limoges, France$$aFabre, Gabin
000190920 700__ $$uUniv Limoges, Fac Pharm, LCSN EA1069, F-87025 Limoges, France$$aTrouillas, Patrick
000190920 700__ $$uUniv Neuchatel, Inst Chem, CH-2000 Neuchatel, Switzerland$$aGiannini, Federico
000190920 700__ $$aFurrer, Julien
000190920 700__ $$uUniv Neuchatel, Inst Chem, CH-2000 Neuchatel, Switzerland$$aSuess-Fink, Georg
000190920 700__ $$aTherrien, Bruno$$uUniv Neuchatel, Inst Chem, CH-2000 Neuchatel, Switzerland
000190920 773__ $$j42$$tDalton Transactions$$k43$$q15457-15463
000190920 909C0 $$xU9$$0252010$$pLCOM
000190920 909CO $$pSB$$particle$$ooai:infoscience.tind.io:190920
000190920 917Z8 $$x135992
000190920 937__ $$aEPFL-ARTICLE-190920
000190920 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000190920 980__ $$aARTICLE