872725-59-2Relevant academic research and scientific papers
Synthesis and structural characterization of a photoresponsive organodirhodium complex with active S-S bonds: [(CpPhRh)2(μ-CH2)2(μ-O2SSO2)] (CpPh = η5-C5Me4Ph)
Miyano, Yousuke,Nakai, Hidetaka,Hayashi, Yoshihito,Isobe, Kiyoshi
, p. 122 - 128 (2007)
A photoresponsive rhodium dinuclear complex having phenyltetramethylcyclopentadienyl (CpPh = η5-C5Me4Ph) and photosensitive dithionite (μ-O2SSO2) ligands, [(CpPhRh)2(μ-CH2)2(μ-O2SSO2)] (1), has been synthesized. The crystal of complex 1 (monoclinic, C2/m (No. 12), a = 24.805(2) A?, b = 29.111(2) A?, c = 10.8475(11) A?, β = 105.9830(7)°, V = 7530.0(12) A?3, Z = 8) consists of two independent molecules, 1-cis and 1-trans, with different arrangement of the CpPh ligands. The flexibility, volume, and shape of the reaction cavities around the dithionite unit of 1-cis and 1-trans in the crystal are discussed. The crystal structures of the precursors of 1, trans-[(CpPhRh)2(μ-Cl)2Cl2] and trans-[(CpPhRh)2(μ-CH2)2Me2], are also reported.
Ligand-Controlled Reactivity and Cytotoxicity of Cyclometalated Rhodium(III) Complexes
Zhang, Wen-Ying,Bridgewater, Hannah E.,Banerjee, Samya,Soldevila-Barreda, Joan J.,Clarkson, Guy J.,Shi, Huayun,Imberti, Cinzia,Sadler, Peter J.
, p. 1052 - 1060 (2020)
We report the synthesis, characterization and cytotoxicity of six cyclometalated rhodium(III) complexes [CpXRh(C^N)Z]0/+, in which CpX = Cp*, Cpph, or Cpbiph, C^N = benzo[h]quinoline, and Z = chloride or pyridine. Three X-ray crystal structures showing the expected “piano-stool” configurations have been determined. The chlorido complexes hydrolyzed faster in aqueous solution, and reacted preferentially with 9-ethyl guanine or glutathione compared to their pyridine analogues. The 1-biphenyl-2,3,4,5-tetramethylcyclopentadienyl complex [CpbiphRh(benzo-[h]quinoline)Cl] (3a) was the most efficient catalyst in coenzyme reduced nicotinamide adenine dinucleotide (NADH) oxidation to NAD+ and induced an elevated level of reactive oxygen species (ROS) in A549 human lung cancer cells. The pyridine complex [CpbiphRh(benzo[h]quinoline)py]+ (3b) was the most potent against A549 lung and A2780 ovarian cancer cell lines, being 5-fold more active than cisplatin towards A549 cells, and acted as a ROS scavenger. This work highlights a ligand-controlled strategy to modulate the reactivity and cytotoxicity of cyclometalated rhodium anticancer complexes.
Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes
Brown, Loren C.,Ressegue, Emily,Merola, Joseph S.
, p. 4014 - 4022 (2017/01/09)
The present work describes the design and synthesis of a series of rhodium and iridium dimers [(η5-ring)MCl]2(μ2-Cl)2 (where (η5-ring)MCl = (η5-Me4C5R)Rh(III)Cl or (η
Half-sandwich rhodium(III) transfer hydrogenation catalysts: Reduction of NAD+ and pyruvate, and antiproliferative activity
Soldevila-Barreda, Joan J.,Habtemariam, Abraha,Romero-Canelón, Isolda,Sadler, Peter J.
, p. 322 - 333 (2015/12/23)
Organometallic complexes have the potential to behave as catalytic drugs. We investigate here Rh(III) complexes of general formula [(Cpx)Rh(N,N′)(Cl)], where N,N′ is ethylenediamine (en), 2,2′-bipyridine (bpy), 1,10-phenanthroline (phen) or N-(
NOVEL IRIDIUM/RHODIUM ANTI-CANCER COMPOUNDS
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Page/Page column 39, (2011/12/14)
The present invention relates to novel iridium and/or rhodium containing complexes for use as a cytotoxic, such as an anti-cancer agent. There is also provided a method of preparing said compounds.
Mechanistic insights into an unprecedented C-C bond activation on a Rh/Ga bimetallic complex: A combined experimental/computational approach
Cadenbach, Thomas,Gemel, Christian,Schmid, Rochus,Fischer, Roland A.
, p. 17068 - 17078 (2007/10/03)
The unusual rearrangement of [RhCp*(GaCp*)(CH3) 2] (1c) to [RhCp*(C5Me4Ga(CH 3)3)] (2) is presented and its mechanism is discussed in detail. 13C MAS NMR spectroscopy revealed that the title reaction proceeds cleanly not only in solution but also in solid state, which supports a unimolecular reaction pathway. On the basis of 1H, 13C, and ROESY NMR spectroscopy as well as isolation and structural elucidation of the hydrolysis product, the compound [RhCp*(endo-η4-C 5Me5GaMe2)] (3a) was identified as a crucial reaction intermediate. DFT calculations on the B3LYP level of theory support this assignment and suggest a concerted C-C bond activation mechanism that topologically takes place at the gallium center. Furthermore, two fluxional processes of the reaction intermediate 3a were studied experimentally as well as by computational methods. First, a mechanism takes place similar to a ring-slipping process that exchanges a GaMe2 group between adjacent ring carbon atoms within the same Cp* ring. This process proceeds at a rate comparable to the NMR time scale and indeed is calculated to be energetically very favorable. Second, a unimolecular exchange process of the GaMe2 group between the two Cp* rings of 3a could be experimentally proven by the introduction of phenyl substituents as a label into the Cp* ligands at both sites, the rhodium as well as the gallium center. A series of experiments including deuteration studies and competition reactions was performed to substantiate the suggested mechanism being in accordance with DFT calculations on possible transition states.
