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1.
Liang He Dr. Si‐Yan Liao Dr. Cai‐Ping Tan Rui‐Rong Ye Yu‐Wen Xu Meng Zhao Prof. Liang‐Nian Ji Prof. Dr. Zong‐Wan Mao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):12152-12160
A series of RuII–arene complexes ( 1 – 6 ) of the general formula [(η6‐arene)Ru(L)Cl]PF6 (arene=benzene or p‐cymene; L=bidentate β‐carboline derivative, an indole alkaloid with potential cyclin‐dependent kinases (CDKs) inhibitory activities) is reported. All the complexes were fully characterized by classical analytical methods, and three were characterized by X‐ray crystallography. Hydrolytic studies show that β‐carboline ligands play a vital role in their aqueous behaviour. These complexes are highly active in vitro, with the most active complex 6 displaying a 3‐ to 12‐fold higher anticancer activity than cisplatin against several cancer cell lines. Interestingly, the complexes are able to overcome cross‐resistance to cisplatin, and show much lower cytotoxicity against normal cells. Complexes 1 – 6 may directly target CDK1, because they can block cells in the G2M phase, down‐regulate the expression of CDK1 and cyclin B1, and inhibit CDK1/cyclin B in vitro. Further mechanism studies show that the complexes can effectively induce apoptosis through mitochondrial‐related pathways and intracellular reactive oxygen species (ROS) elevation. 相似文献
2.
Selenoquinones Stabilized by Ruthenium(II) Arene Complexes: Synthesis,Structure, and Cytotoxicity 下载免费PDF全文
Dr. Julien Dubarle‐Offner Catherine M. Clavel Geoffrey Gontard Prof. Paul J. Dyson Dr. Hani Amouri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(19):5795-5801
A new series of monoselenoquinone and diselenoquinone π complexes, [(η6‐p‐cymene)Ru(η4‐C6R4SeE)] (R=H, E=Se ( 6 ); R=CH3, E=Se ( 7 ); R=H, E=O ( 8 )), as well as selenolate π complexes [(η6‐p‐cymene)Ru(η5‐C6H3R2Se)][SbF6] (R=H ( 9 ); R=CH3 ( 10 )), stabilized by arene ruthenium moieties were prepared in good yields through nucleophilic substitution reactions from dichlorinated‐arene and hydroxymonochlorinated‐arene ruthenium complexes [(η6‐p‐cymene)Ru(C6R4XCl)][SbF6]2 (R=H, X=Cl ( 1 ); R=CH3, X=Cl ( 2 ); R=H, X=OH ( 3 )) as well as the monochlorinated π complexes [(η6‐p‐cymene)Ru(η5‐C6H3R2Cl)][SbF6]2 (R=H ( 4 ); R=CH3 ( 5 )). The X‐ray crystallographic structures of two of the compounds, [(η6‐p‐cymene)Ru(η4‐C6Me4Se2)] ( 7 ) and [(η6‐p‐cymene)Ru(η4‐C6H4SeO)] ( 8 ), were determined. The structures confirm the identity of the target compounds and ascertain the coordination mode of these unprecedented ruthenium π complexes of selenoquinones. Furthermore, these new compounds display relevant cytotoxic properties towards human ovarian cancer cells. 相似文献
3.
《应用有机金属化学》2017,31(7)
Neutral half‐sandwich η6‐p ‐cymene ruthenium(II) complexes of general formula [Ru(η6‐p ‐cymene)Cl(L)] (HL = monobasic O, N bidendate benzoylhydrazone ligand) have been synthesized from the reaction of [Ru(η6‐p ‐cymene)(μ‐Cl)Cl]2 with acetophenone benzoylhydrazone ligands. All the complexes have been characterized using analytical and spectroscopic (Fourier transform infrared, UV–visible, 1H NMR, 13C NMR) techniques. The molecular structures of three of the complexes have been determined using single‐crystal X‐ray diffraction, indicating a pseudo‐octahedral geometry around the ruthenium(II) ion. All the ruthenium(II) arene complexes were explored as catalysts for transfer hydrogenation of a wide range of aromatic, cyclic and aliphatic ketones with 2‐propanol using 0.1 mol% catalyst loading, and conversions of up to 100% were obtained. Further, the influence of other variables on the transfer hydrogenation reaction, such as base, temperature, catalyst loading and substrate scope, was also investigated. 相似文献
4.
Reactions of pyrazole based ligand and halide bridged arene d6 metal precursors resulted a series of mono and di‐substituted pyrazole based half sandwich d6 metal complexes. In general, they are formulated as [(arene)MLCl2] [M = Ru, arene = benzene ( 1 ), p‐cymene ( 2 ), arene = Cp*, M = Rh ( 3 ) and Ir ( 4 )] and [(arene)ML2Cl] [M = Ru, arene = benzene ( 5 ), p‐cymene ( 6 ), arene = Cp*, M = Rh ( 7 ) and Ir ( 8 )]. All these complexes were characterized by various spectroscopic techniques (IR, 1H NMR, ESI‐MS, and UV/Vis). The molecular structures were confirmed by single‐crystal X‐ray diffraction technique. Spectroscopic studies revealed that complexation i.e., mono‐ and di‐substitution occurred by the ratio‐based reaction between pyrazole ligand and metal precursor through the neutral nitrogen rather than protic nitrogen. In these complexes deprotonation of the protic nitrogen does not occur unlike the other complexes containing pyrazole derivatives, in which the pyrazole ligand is anionic. 相似文献
5.
Chinky Binnani Deepika Tyagi Rohit K. Rai Dr. Shaikh M. Mobin Dr. Sanjay K. Singh 《化学:亚洲杂志》2016,11(21):3022-3031
Water‐soluble arene–ruthenium complexes coordinated with readily available aniline‐based ligands were successfully employed as highly active catalysts in the C?H bond activation and arylation of 2‐phenylpyridine with aryl halides in water. A variety of (hetero)aryl halides were also used for the ortho‐C?H bond arylation of 2‐phenylpyridine to afford the corresponding ortho‐ monoarylated products as major products in moderate to good yields. Our investigations, including time‐scaled NMR spectroscopy and mass spectrometry studies, evidenced that the coordinating aniline‐based ligands, having varying electronic and steric properties, had a significant influence on the catalytic activity of the resulting arene–ruthenium–aniline‐based complexes. Moreover, mass spectrometry identification of the cycloruthenated species, {(η6‐arene)Ru(κ2‐C,N‐phenylpyridine)}+, and several ligand‐coordinated cycloruthenated species, such as [(η6‐arene)Ru(4‐methylaniline)(κ2‐C,N‐phenylpyridine)]+, found during the reaction of 2‐phenylpyridine with the arene–ruthenium–aniline complexes further authenticated the crucial roles of these species in the observed highly active and tuned catalyst. At last, the structures of a few of the active catalysts were also confirmed by single‐crystal X‐ray diffraction studies. 相似文献
6.
Govindasamy Vinoth Sekar Indira Madheswaran Bharathi Anandhan Durgadevi Ravikumar Abinaya Luis G. Alves Ana Margarida Martins Kuppannan Shanmuga Bharathi 《应用有机金属化学》2019,33(11)
A new class of half‐sandwich (η6‐p‐cymene) ruthenium(II) complexes supported by 2‐aminofluorene derivatives [Ru(η6‐p‐cymene)(Cl)(L)] ( L = 2‐(((9H‐fluoren‐2‐yl)imino)methyl)phenol ( L 1 ), 2‐(((9H‐fluoren‐2‐yl)imino)methyl)‐3‐methoxyphenol ( L 2 ), 1‐(((9H‐fluoren‐2‐yl)imino)methyl)naphthalene‐2‐ol ( L 3 ) and N‐((1H‐pyrrol‐2‐yl)methylene)‐9H‐fluorene‐2‐amine ( L 4 )) were synthesized. All compounds were fully characterized by analytical and spectroscopic techniques (IR, UV–Vis, NMR) and also by mass spectrometry. The solid state molecular structures of the complexes [Ru(η6‐p‐cymene)(Cl)(L2)], [Ru(η6‐p‐cymene)(Cl)(L3)] and [Ru(η6‐p‐cymene)(Cl)(L4)] revealed that the 2‐aminofluorene and p‐cymene moieties coordinate to ruthenium(II) in a three‐legged piano‐stool geometry. The synthesized complexes were used as catalysts for the dehydrogenative coupling of benzyl alcohol with a range of amines (aliphatic, aromatic and heterocyclic). The reactions were carried out under thermal heating, ultrasound and microwave assistance, using solvent or solvent free conditions, and the catalytic performance was optimized regarding the solvent, the type of base, the catalyst loading and the temperature. Moderately high to very high isolated yields were obtained using [Ru(η6‐p‐cymene)(Cl)(L4)] at 1 mol%. In general, microwave irradiation produced better yields than the other two techniques irrespective of the nature of the substituents. 相似文献
7.
Novel cyclohexyl‐based aminophosphine ligands and use of their Ru(II) complexes in transfer hydrogenation of ketones 下载免费PDF全文
Cezmi Kayan Nermin Meriç Murat Aydemir Yusuf Selim Ocak Ak𝚤n Baysal Hamdi Temel 《应用有机金属化学》2014,28(2):127-133
Two new aminophosphines – furfuryl‐(N‐dicyclohexylphosphino)amine, [Cy2PNHCH2–C4H3O] ( 1 ) and thiophene‐(N‐dicyclohexylphosphino)amine, [Cy2PNHCH2–C4H3S] ( 2 ) – were prepared by the reaction of chlorodicyclohexylphosphine with furfurylamine and thiophene‐2‐methylamine. Reaction of the aminophosphines with [Ru(η6‐p‐cymene)(μ‐Cl)Cl]2 or [Ru(η6‐benzene)(μ‐Cl)Cl]2 gave corresponding complexes [Ru(Cy2PNHCH2–C4H3O)(η6‐p‐cymene)Cl2] ( 1a ), [Ru(Cy2PNHCH2–C4H3O)(η6‐benzene)Cl2] ( 1b ), [Ru(Cy2PNHCH2–C4H3S)(η6‐p‐cymene)Cl2] ( 2a ) and [Ru(Cy2PNHCH2–C4H3S)(η6‐benzene)Cl2] ( 2b ), respectively, which are suitable catalyst precursors for the transfer hydrogenation of ketones. In particular, [Ru(Cy2PNHCH2–C4H3S)(η6‐benzene)Cl2] acts as a good catalyst, giving the corresponding alcohols in 98–99% yield in 30 min at 82 °C (up to time of flight ≤ 588 h?1). Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
8.
Durairaj Gopalakrishnan Santhanam Srinath Baburaj Baskar Nattamai S.P. Bhuvanesh Mani Ganeshpandian 《应用有机金属化学》2019,33(3)
Two organometallic Ru(II)‐p‐cymene complexes of the type [Ru(η6‐p‐cymene)(L)Cl]PF6 1 and 2 , where L is N,N‐bis(4‐isopropylbenzylidene)ethane‐1,2‐diamine (bien, L1 ) or N,N‐bis (pyren‐2‐ylmethylene)ethane‐1,2‐diamine (bpen, L2 ) have been prepared and characterized well. Because of appended pyrenyl groups in coordinated bpen ligand, the complex 2 exhibits higher DNA and protein binding than complex 1 in which isopropylbenzyl groups are incorporated. Interestingly, the luminescent characteristic complex 2 is unique in displaying DNA cleavage after light activation by UVA light at 365 nm through oxygen dependent mechanism. AFM analysis attests the photo‐induced DNA fragmentation ability of complex 2 . Also, the complex 2 cleaves the protein after light exposure in a non‐specific manner suggesting that it can act as a protein photo cleaving agent. In contrast to the trend of DNA and protein interaction of complexes, the complex 1 exhibits cytotoxic activity against human breast carcinoma ( MCF‐7 ) and liver carcinoma ( HepG2 ) with potency higher than that of complex 2 due to enhanced hydrophobicity of isopropyl groups present in p‐cymene and bien ligands. Indeed, complex 2 is inactive against MCF‐7 and HepG2 cancer cell lines even up to 200 μM concentration. The AO/EB staining assay reveals that the complex 1 is able to induce late apoptotic mode of cell death in breast cancer cells, which is further confirmed by inter‐nucleosomal DNA cleavage. Furthermore, the complexes 1 and 2 are evaluated for their catalytic activities and found to be working well for the β‐carboline directed C–H arylation to afford the desired products in good yield (40–47%). 相似文献
9.
Influence of Halogen Substitution in the Ligand Sphere on the Antitumor and Antibacterial Activity of Half‐sandwich Ruthenium(II) Complexes [RuX(η6‐arene)(C5H4N‐2‐CH=N‐Ar)]+ 下载免费PDF全文
Joel M. Gichumbi Bernard Omondi Geraldine Lazarus Moganavelli Singh Nazia Shaikh Hafizah Y. Chenia Holger B. Friedrich 《无机化学与普通化学杂志》2017,643(11):699-711
New complexes [(η6‐p‐cymene)Ru(C5H4N‐2‐CH=N–Ar)X]PF6 [X = Br ( 1 ), I ( 2 ); Ar = 4‐fluorophenyl ( a ), 4‐chlorophenyl ( b ), 4‐bromophenyl ( c ), 4‐iodophenyl ( d ), 2,5‐dichlorophenyl ( e )] were prepared, as well as 3a – 3e (X = Cl) and the new complexes [(η6‐arene)RuCl(N‐N)]PF6 (arene = C6H5OCH2CH2OH, N‐N = 2,2′‐bipyridine ( 4 ), 2,6‐(dimethylphenyl)‐pyridin‐2‐yl‐methylene amine ( 5 ), 2,6‐(diisopropylphenyl)‐pyridin‐2‐yl‐methylene amine ( 6 ); arene = p‐cymene, N‐N = 4‐(aminophenyl)‐pyridin‐2‐yl‐methylene amine ( 7 )]. X‐ray diffraction studies were performed for 1a , 1b , 1c , 1d , 2b , 5 , and 7 . Cytotoxicities of 1a – 1d and 2 were established versus human cancer cells epithelial colorectal adenocarcinoma (Caco‐2) (IC50: 35.8–631.0 μM), breast adenocarcinoma (MCF7) (IC50: 36.3–128.8.0 μM), and hepatocellular carcinoma (HepG2) (IC50: 60.6–439.8 μM), 3a – 3e were tested against HepG2 and Caco‐2, and 4 – 7 were tested against Caco‐2. 1 – 7 were tested against non‐cancerous human epithelial kidney cells. 1 and 2 were more selective towards tumor cells than the anticancer drug 5‐fluorouracil (5‐FU), but 3a – 3e (X = Cl) were not selective. 1 and 2 had good activity against MCF7, some with lower IC50 than 5‐FU. Complexes with X = Br or I had moderate activity against Caco‐2 and HepG2, but those with Cl were inactive. Antibacterial activities of 1a , 2b , 3a , and 7 were tested against antibacterial susceptible and resistant Gram‐negative and ‐positive bacteria. 1a , 2b , and 3a showed activity against methicillin‐resistant S. aureus (MIC = 31–2000 μg · mL–1). 相似文献
10.
Synthesis,cytotoxicity and anti‐metastatic properties of new pyridyl–thiazole arene ruthenium(II) complexes 下载免费PDF全文
A series of novel ruthenium(II)–cymene complexes ( 1 – 8 ) containing substituted pyridyl–thiazole ligands, [Ru(η6‐p‐cymene)(L)Cl]Cl (L = N,N‐chelating derivatives), have been synthesized and characterized using elemental analysis, infrared, 1H NMR and 13C NMR spectroscopies and mass spectrometry. All these complexes not only display marked cytotoxicity in vitro against three different human cancer cell lines (HeLa, A549 and MDA‐MB‐231), but also exhibit promising anti‐metastatic activity at sub‐cytotoxic concentrations. Cell cycle analysis shows that the ruthenium(II) complex‐induced growth inhibition was mainly caused by S‐phase cell cycle arrest. Further protein level analysis suggests that compound 5 may exert antitumor activity via a p53‐independent mechanism. 相似文献
11.
Neutral and cationic half‐sandwich arene d6 metal complexes containing pyridyl and pyrimidyl thiourea ligands with interesting bonding modes: Synthesis,structural and anti‐cancer studies 下载免费PDF全文
Sanjay Adhikari Omar Hussain Roger M. Phillips Werner Kaminsky Mohan Rao Kollipara 《应用有机金属化学》2018,32(9)
The reaction of [(p‐cymene)RuCl2]2 and [Cp*MCl2]2 (M = Rh/Ir) with benzoyl (2‐pyrimidyl) thiourea (L1) and benzoyl (4‐picolyl) thiourea (L2) led to the formation of cationic complexes bearing formula [(arene) M (L1)к2 (N,S) Cl]+ and [(arene) M (L2)к2(N,S)Cl]+ [(arene) = p‐cymene, M = Ru, ( 1 , 4 ); Cp*, M = Rh ( 2 , 5 ) and Ir ( 3 , 6 )]. Precursor compounds reacted with benzoyl (6‐picolyl) thiourea (L3) affording neutral complexes having formula [(arene) M (L3)к1(S)Cl2] [arene = p‐cymene, M = Ru, ( 7 ); Cp*, M = Rh ( 8 ), Ir ( 9 )]. X‐ray studies revealed that the methyl substituent attached to the pyridine ring in ligands L2 and L3 affects its coordination mode. When methyl group is at the para position of the pyridine ring (L2), the ligand coordinated metal in a bidentate chelating N, S‐ mode whereas methyl group at ortho position (L3), it coordinated in a monodentate mode. Further the anti‐cancer studies of the thiourea derivatives and its complexes carried out against HCT‐116, HT‐29 (human colorectal cancer), Mia‐PaCa‐2 (human pancreatic cancer) and ARPE‐19 (non‐cancer retinal epithelium) cell lines showed that the thiourea ligands are inactive but upon complexation, the metal compounds displayed potent and selective activity against cancer cells in vitro. Iridium complexes were found to be more potent as compared to ruthenium and rhodium complexes. 相似文献
12.
Reaction of [Ru(η6‐p‐cymene)Cl2]2 with two equivalents of [Ph4P][Cl] in CH2Cl2 yields [Ph4P][Ru(η6‐p‐cymene)Cl3], containing a trichlororuthenate(II) anion. In solution, an equilibrium between the product and [Ru(η6‐p‐cymene)Cl2]2 is observed, which in CDCl3 is nearly completely shifted to the dimer, whereas in CD2Cl2 essentially a 1:1‐mixture of the two ruthenium species is present. Crystallization from CH2Cl2/pentane yielded two different crystals, which were identified by X‐ray analysis as [Ph4P][Ru(η6‐p‐cymene)Cl3] and [Ph4P][Ru(η6‐p‐cymene)Cl3]·CH2Cl2. 相似文献
13.
Christian A. Sandoval Dr. Fusheng Bie Aki Matsuoka Yoshiki Yamaguchi Dr. Hiroshi Naka Prof. Dr. Yuehui Li Koichi Kato Prof. Dr. Noriyuki Utsumi Kunihiko Tsutsumi Takeshi Ohkuma Prof. Dr. Kunihiko Murata Dr. Ryoji Noyori Prof. Dr. 《化学:亚洲杂志》2010,5(4):806-816
Aromatic ketones are enantioseletively hydrogenated in alcohols containing [RuX{(S,S)‐Tsdpen}(η6‐p‐cymene)] (Tsdpen=TsNCH(C6H5)CH(C6H5)NH2; X=TfO, Cl) as precatalysts. The corresponding Ru hydride (X=H) acts as a reducing species. The solution structures and complete spectral assignment of these complexes have been determined using 2D NMR (1H‐1H DQF‐COSY, 1H‐13C HMQC, 1H‐15N HSQC, and 1H‐19F HOESY). Depending on the nature of the solvents and conditions, the precatalysts exist as a covalently bound complex, tight ion pair of [Ru+(Tsdpen)(cymene)] and X?, solvent‐separated ion pair, or discrete free ions. Solvent effects on the NH2 chemical shifts of the Ru complexes and the hydrodynamic radius and volume of the Ru+ and TfO? ions elucidate the process of precatalyst activation for hydrogenation. Most notably, the Ru triflate possessing a high ionizability, substantiated by cyclic voltammetry, exists in alcoholic solvents largely as a solvent‐separated ion pair and/or free ions. Accordingly, its diffusion‐derived data in CD3OD reflect the independent motion of [Ru+(Tsdpen)(cymene)] and TfO?. In CDCl3, the complex largely retains the covalent structure showing similar diffusion data for the cation and anion. The Ru triflate and chloride show similar but distinct solution behavior in various solvents. Conductivity measurements and catalytic behavior demonstrate that both complexes ionize in CH3OH to generate a common [Ru+(Tsdpen)(cymene)] and X?, although the extent is significantly greater for X=TfO?. The activation of [RuX(Tsdpen)(cymene)] during catalytic hydrogenation in alcoholic solvent occurs by simple ionization to generate [Ru+(Tsdpen)(cymene)]. The catalytic activity is thus significantly influenced by the reaction conditions. 相似文献
14.
Synthesis,structural and chemosensitivity studies of arene d6 metal complexes having N‐phenyl‐N´‐(pyridyl/pyrimidyl)thiourea derivatives 下载免费PDF全文
Sanjay Adhikari Omar Hussain Roger M. Phillips Werner Kaminsky Mohan Rao Kollipara 《应用有机金属化学》2018,32(6)
The d6 metal complexes of thiourea derivatives were synthesized to investigate its cytotoxicity. Treatment of various N‐phenyl‐N´ pyridyl/pyrimidyl thiourea ligands with half‐sandwich d6 metal precursors yielded a series of cationic complexes. Reactions of ligand (L1‐L3) with [(p‐cymene)RuCl2]2 and [Cp*MCl2]2 (M = Rh/Ir) led to the formation of a series of cationic complexes bearing general formula [(arene)M(L1)к2(N,S)Cl]+, [(arene)M(L2)к2(N,S)Cl]+ and [(arene)M(L3)к2(N,S)Cl]+ [arene = p‐cymene, M = Ru ( 1 , 4 , 7 ); Cp*, M = Rh ( 2 , 5 , 8 ); Cp*, Ir ( 3 , 6 , 9 )]. These compounds were isolated as their chloride salts. X‐ray crystallographic studies of the complexes revealed the coordination of the ligands to the metal in a bidentate chelating N,S‐ manner. Further the cytotoxicity studies of the thiourea derivatives and its complexes evaluated against HCT‐116 (human colorectal cancer), MIA‐PaCa‐2 (human pancreatic cancer) and ARPE‐19 (non‐cancer retinal epithelium) cancer cell lines showed that the thiourea ligands displayed no activity. Upon complexation however, the metal compounds possesses cytotoxicity and whilst potency is less than cisplatin, several complexes exhibited greater selectivity for HCT‐116 or MIA‐PaCa‐2 cells compared to ARPE‐19 cells than cisplatin in vitro. Rhodium complexes of thiourea derivatives were found to be more potent as compared to ruthenium and iridium complexes. 相似文献
15.
Dr. Samuel M. Meier Maria Novak Dr. Wolfgang Kandioller Dr. Michael A. Jakupec Prof. Dr. Vladimir B. Arion Prof. Dr. Nils Metzler‐Nolte Prof. Dr. Bernhard K. Keppler Prof. Dr. Christian G. Hartinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(28):9297-9307
Organometallic Ru(arene)–peptide bioconjugates with potent in vitro anticancer activity are rare. We have prepared a conjugate of a Ru(arene) complex with the neuropeptide [Leu5]‐enkephalin. [Chlorido(η6‐p‐cymene)(5‐oxo‐κO‐2‐{(4‐[(N‐tyrosinyl‐glycinyl‐glycinyl‐phenylalanyl‐leucinyl‐NH2)propanamido]‐1H‐1,2,3‐triazol‐1‐yl)methyl}‐4H‐pyronato‐κO)ruthenium(II)] ( 8 ) shows antiproliferative activity in human ovarian carcinoma cells with an IC50 value as low as 13 μM , whereas the peptide or the Ru moiety alone are hardly cytotoxic. The conjugation strategy for linking the Ru(cym) (cym=η6‐p‐cymene) moiety to the peptide involved N‐terminal modification of an alkyne‐[Leu5]‐enkephalin with a 2‐(azidomethyl)‐5‐hydroxy‐4H‐pyran‐4‐one linker, using CuI‐catalyzed alkyne–azide cycloaddition (CuAAC), and subsequent metallation with the Ru(cym) moiety. The ruthenium‐bioconjugate was characterized by high resolution top‐down electrospray ionization mass spectrometry (ESI‐MS) with regard to peptide sequence, linker modification and metallation site. Notably, complete sequence coverage was obtained and the Ru(cym) moiety was confirmed to be coordinated to the pyronato linker. The ruthenium‐bioconjugate was analyzed with respect to cytotoxicity‐determining constituents, and through the bioconjugate models [{2‐(azidomethyl)‐5‐oxo‐κO‐4H‐pyronato‐κO}chloride (η6‐p‐cymene)ruthenium(II)] ( 5 ) and [chlorido(η6‐p‐cymene){5‐oxo‐κO‐2‐([(4‐(phenoxymethyl)‐1H‐1,2,3‐triazol‐1‐yl]methyl)‐4H‐pyronato‐κO}ruthenium(II)] ( 6 ) the Ru(cym) fragment with a triazole‐carrying pyronato ligand was identified as the minimal unit required to achieve in vitro anticancer activity. 相似文献
16.
Osman Dayan Muharrem Diner Bekir etinkaya Namk
zdemir Orhan Büyükgüngr 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(8):m346-m348
The title complex, di‐μ‐chloro‐bis[chloro(η6‐p‐cymene)ruthenium(II)]–9H‐carbazole (1/2), [Ru2Cl4(C10H14)2]·2C12H9N, is composed of one [RuCl2(η6‐p‐cymene)]2 and two 9H‐carbazole molecules. There are one‐half of a dinuclear complex and one 9H‐carbazole molecule per asymmetric unit. In the dinuclear complex, each of the two crystallographically equivalent Ru atoms is in a pseudo‐tetrahedral environment, coordinated by a terminal Cl atom, two bridging Cl atoms and the aromatic hydrocarbon, which is linked in a η6 manner; the Ru⋯Ru separation is 3.688 (3) Å. The title complex has a crystallographic centre of symmetry located at the mid‐point of the Ru⋯Ru line. Intermolecular N—H⋯Cl and π–π stacking interactions are observed. These interactions form a four‐pointed star‐shaped ring and one‐dimensional linear chains of edge‐fused rings running parallel to the [100] direction, which stabilize the crystal packing. 相似文献
17.
Synthesis,structure and antiproliferative activity of dinuclear ruthenium arene complexes with differently coordinated thiosemicarbazones 下载免费PDF全文
A series of di‐nuclear ruthenium arene complexes with TSC ligands ([(η6‐p‐cymene)Ru(N1,S‐TSC)]2Cl2, A‐type, 1 and 2 ) and their corresponding analogues ([(η6‐p‐cymene)Ru(N2,S‐TSC)]2Cl2, B‐type, 3 and 4 ), in which TSCs act as different coordination mode, have been synthesized and structurally characterized by a variety of physical methods. The molecular structures of 1 , 3 and 4 were determined using single‐crystal X‐ray diffraction analysis. The Gibbs free energy of the two examples of the two types of complexes ( 1 and 3 ) and bonding order in their single‐crystals were discussed using density functional theory (DFT) calculations. The compounds were further evaluated for their in vitro antiproliferative activities against several cancerous and HEK‐293 T noncancerous cell lines, and the results indicate that B‐type complexes show stronger cytotoxicity than A‐type complexes. Furthermore, the interactions of the compounds with DNA were investigated by electrophoretic mobility spectrometry studies. 相似文献
18.
Quan Zhou Peiyuan Li Rumei Lu Quanquan Qian Xiaolin Lei Qi Xiao Shan Huang Lifeng Liu Chusheng Huang Wei Su 《无机化学与普通化学杂志》2013,639(6):943-946
An organometallic salt composed of a new cationic p‐cymene ruthenium chloro complex containing a chelating benzaldehyde semicarbazone ligand and of the known anionic p‐cymene ruthenium trichloro complex, [(η6‐p‐cymene)Ru(bzsc)Cl]+[(η6‐p‐cymene)RuCl3]– ( 1 ) (bzsc = benzaldehyde semicarbazone) was synthesized and further characterized by IR, 1H NMR, and UV/Vis spectroscopy HR‐ESI mass spectrometry, and elemental analysis. The single‐crystal structure of 1 was also determined. The in vitro anticancer activities of the complex was evaluated against three human cancer cell lines (SGC‐7901, BEL‐7404 and CNE‐1), and the IC50 values were 20.7, 71.1 and 42.6 μM, respectively. 相似文献
19.
Ruthenium(II) Phthalocyaninates(2–): Synthesis and Properties of (Acido)(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc2?]? (X = Cl, Br, I, NCO, NCS, N3) (nBu4N)[Ru(OH)2Pc2?] is reduced in acetone with carbonmonoxid to blue-violet [Ru(H2O)(CO)Pc2?], which yields in tetrahydrofurane with excess (nBu4N)X acido(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc2?]? (X = Cl, Br, I, NCO, NCS, N3) isolated as red-violet, diamagnetic (nBu4N) complex salt. The UV-Vis spectra are dominated by the typical π-π* transitions of the Pc2? ligand at approximately 15100 (B), 28300 (Q1) und 33500 cm?1 (Q2), only fairly dependent of the axial ligands. v(C? O) is observed at 1927 (X = I), 1930 (Cl, Br), 1936 (N3, NCO) 1948 cm?1 (NCS), v(C? N) at 2208 cm?1 (NCO), 2093 cm?1 (NCS) and v(N? N) at 2030 cm?1 only in the MIR spectrum. v(Ru? C) coincides in the FIR spectrum with a deformation vibration of the Pc ligand, but is detected in the resonance Raman(RR) spectrum at 516 (X = Cl), 512 (Br), 510 (N3), 504 (I), 499 (NCO), 498 cm?1 (NCS). v(Ru? X) is observed in the FIR spectrum at 257 (X = Cl), 191 (Br), 166 (I), 349 (N3), 336 (NCO) and 224 cm?1 (NCS). Only v(Ru? I) is RR-enhanced. 相似文献
20.
Wolfgang Kandioller Dr. Christian G. Hartinger Dr. Alexey A. Nazarov Dr. Caroline Bartel Matthias Skocic Michael A. Jakupec Dr. Vladimir B. Arion Prof. Bernhard K. Keppler Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(45):12283-12291
Organometallic ruthenium–arene compounds bearing a maltol ligand have been shown to be nearly inactive in in vitro anticancer assays, presumably due to the formation of dimeric RuII species in aqueous solutions. In an attempt to stabilize such complexes, [Ru(η6‐p‐cymene)(XY)Cl] (XY=pyrones or thiopyrones) complexes with different substitution pattern of the (thio)pyrone ligands have been synthesized, their structures characterized spectroscopically, and their aquation behavior investigated as well as their tumor‐inhibiting potency. The aquation behavior of pyrone systems with electron‐donating substituents and of thiopyrone complexes was found to be significantly different from that of the maltol‐type complex reported previously. However, the formation of the dimer can be excluded as the primary reason for the inactivity of the complex because some of the stable compounds are not active in cancer cell lines either. In contrast, studies of their reactivity towards amino acids demonstrate different reactivities of the pyrone and thiopyrone complexes, and the higher stability of the latter probably renders them active against human tumor cells. 相似文献