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1.
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
2.
《应用有机金属化学》2017,31(7)
Half‐sandwich ruthenium, rhodium and iridium complexes ( 1 – 12 ) were synthesized with aldoxime ( L1 ), ketoxime ( L2 ) and amidoxime ( L3 ) ligands. Ligands have the general formula [PyC(R)NOH], where R = H ( L1 ), R = CH3 ( L2 ) and R = NH2 ( L3 ). Reaction of [{(arene)MCl2}2] (arene = p ‐cymene, benzene, Cp*; M = Ru, Rh, Ir) with ligands L1 – L3 in 1:2 metal precursor‐to‐ligand ratio yielded complexes such as [{(arene)MLκ2(N∩N)Cl}]PF6. All the ligands act as bidentate chelating nitrogen donors in κ2(N∩N) fashion while forming complexes. In vitro anti‐tumour activity of complexes 2 and 10 against HT‐29 (human colorectal cancer), BE (human colorectal cancer) and MIA PaCa‐2 (human pancreatic cancer) cell lines and non‐cancer cell line ARPE‐19 (human retinal epithelial cells) revealed a comparable activity although complex 2 demonstrated greater selectivity for MIA PaCa‐2 cells than cisplatin. Further studies demonstrated that complexes 3 , 6 , 9 and 12 induced significant apoptosis in Dalton's ascites lymphoma (DL) cells. In vivo anti‐tumour activity of complex 2 on DL‐bearing mice revealed a statistically significant anti‐tumour activity (P = 0.0052). Complexes 1 – 12 exhibit HOMO–LUMO energy gaps from 3.31 to 3.68 eV. Time‐dependent density functional theory calculations explain the nature of electronic transitions and were in good agreement with experiments. 相似文献
3.
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
4.
Study of the Bonding Modes of Di‐2‐pyridyl ketoxime Ligand towards Ruthenium,Rhodium and Iridium Half Sandwich Complexes 下载免费PDF全文
The bonding modes of the ligand di‐2‐pyridyl ketoxime towards half‐sandwich arene ruthenium, Cp*Rh and Cp*Ir complexes were investigated. Di‐2‐pyridyl ketoxime {pyC(py)NOH} react with metal precursor [Cp*IrCl2]2 to give cationic oxime complexes of the general formula [Cp*Ir{pyC(py)NOH}Cl]PF6 ( 1a ) and [Cp*Ir{pyC(py)NOH}Cl]PF6 ( 1b ), for which two coordination isomers were observed by NMR spectroscopy. The molecular structures of the complexes revealed that in the major isomer the oxime nitrogen and one of the pyridine nitrogen atoms are coordinated to the central iridium atom forming a five membered metallocycle, whereas in the minor isomer both the pyridine nitrogen atoms are coordinated to the iridium atom forming a six membered metallacyclic ring. Di‐2‐pyridyl ketoxime react with [(arene)MCl2]2 to form complexes bearing formula [(p‐cymene)Ru{pyC(py)NOH}Cl]PF6 ( 2 ); [(benzene)Ru{pyC(py)NOH}Cl]PF6 ( 3 ), and [Cp*Rh{pyC(py)NOH}Cl]PF6 ( 4 ). In case of complex 3 the ligand coordinates to the metal by using oxime nitrogen and one of the pyridine nitrogen atoms, whereas in complex 4 both the pyridine nitrogen atoms are coordinated to the metal ion. The complexes were fully characterized by spectroscopic techniques. 相似文献
5.
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
6.
Four‐Membered Heterometallacyclic d0 and d1 Complexes of Group 4 Metallocenes with Amidato Ligands 下载免费PDF全文
Dr. Martin Haehnel Jacqueline B. Priebe Jacky C.‐H. Yim Dr. Anke Spannenberg Prof. Dr. Angelika Brückner Prof. Dr. Laurel L. Schafer Prof. Dr. Uwe Rosenthal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7752-7758
A study of the coordination chemistry of different amidato ligands [(R)N?C(Ph)O] (R=Ph, 2,6‐diisopropylphenyl (Dipp)) at Group 4 metallocenes is presented. The heterometallacyclic complexes [Cp2M(Cl){κ2‐N,O‐(R)N?C(Ph)O}] M=Zr, R=Dipp ( 1 a ), Ph ( 1 b ); M=Hf, R=Ph ( 2 )) were synthesized by reaction of [Cp2MCl2] with the corresponding deprotonated amides. Complex 1 a was also prepared by direct deprotonation of the amide with Schwartz reagent [Cp2Zr(H)Cl]. Salt metathesis reaction of [Cp2Zr(H)Cl] with deprotonated amide [(Dipp)N?C(Ph)O] gave the zirconocene hydrido complex [Cp2M(H){κ2‐N,O‐(Dipp)N?C(Ph)O}] ( 3 ). Reaction of 1 a with Mg did not result in the desired Zr(III) complex but in formation of Mg complex [(py)3Mg(Cl) {κ2‐N,O‐(Dipp)N?C(Ph)O}] ( 4 ; py=pyridine). The paramagnetic complexes [Cp′2Ti{κ2‐N,O‐(R)N?C(Ph)O}] (Cp′=Cp, R=Ph ( 7 a ); Cp′=Cp, R=Dipp ( 7 b ); Cp′=Cp*, R=Ph ( 8 )) were prepared by the reaction of the known titanocene alkyne complexes [Cp2′Ti(η2‐Me3SiC2SiMe3)] (Cp′=Cp ( 5 ), Cp′=Cp* ( 6 )) with the corresponding amides. Complexes 1 a , 2 , 3 , 4 , 7 a , 7 b , and 8 were characterized by X‐ray crystallography. The structure and bonding of complexes 7 a and 8 were also characterized by EPR spectroscopy. 相似文献
7.
Piano‐stool‐shaped platinum group metal compounds, stable in the solid state and in solution, which are based on 2‐(5‐phenyl‐1H‐pyrazol‐3‐yl)pyridine ( L ) with the formulas [(η6‐arene)Ru( L )Cl]PF6 {arene = C6H6 ( 1 ), p‐cymene ( 2 ), and C6Me6, ( 3 )}, [(η6‐C5Me5)M( L )Cl]PF6 {M = Rh ( 4 ), Ir ( 5 )}, and [(η5‐C5H5)Ru(PPh3)( L )]PF6 ( 6 ), [(η5‐C5H5)Os(PPh3)( L )]PF6 ( 7 ), [(η5‐C5Me5)Ru(PPh3)( L )]PF6 ( 8 ), and [(η5‐C9H7)Ru(PPh3)( L )]PF6 ( 9 ) were prepared by a general method and characterized by NMR and IR spectroscopy and mass spectrometry. The molecular structures of compounds 4 and 5 were established by single‐crystal X‐ray diffraction. In each compound the metal is connected to N1 and N11 in a k2 manner. 相似文献
8.
《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
9.
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
10.
Organometallic 5d6 Transition Metal Complexes of 1‐Methyl‐(2‐alkylthiomethyl)‐1H‐benzimidazole Ligands: Structures and Electrochemical Oxidation The complexes [(mmb)Re(CO)3Cl], [(mtb)Re(CO)3Cl], [(mmb)OsCl(Cym)](PF6) and [(Cym)OsCl(mtb)](PF6) where Cym = p‐cymene, mmb = 1‐methyl‐(2‐methylthiomethyl)‐1H‐benzimidazole and mtb = 1‐methyl‐(2‐tert‐butylthiomethyl)‐1H‐benzimidazole were synthesized and, except for the latter, structurally characterized. In comparison with other late transition metal compounds of these N‐S chelate ligands the rhenium(I) systems exhibit a balanced coordination to both N and S donor atoms. Anodic one‐electron oxidation produces EPR‐silent rhenium(II) states whereas the osmium(III) species [(mmb)OsCl(Cym)]2+ could be identified via EPR and UV/VIS spectroelectrochemistry. 相似文献
11.
Metal Complexes of Biologically Important Ligands, CLVII [1] Halfsandwich Complexes of Isocyanoacetylamino acid esters and of Isocyanoacetyldi‐ and tripeptide esters (?Isocyanopeptides”?) N‐Isocyanoacetyl‐amino acid esters CNCH2C(O) NHCH(R)CO2CH3 (R = CH3, CH(CH3)2, CH2CH(CH3)2, CH2C6H5) and N‐isocyanoacetyl‐di‐ and tripeptide esters CNCH2C(O)NHCH(R1)C(O)NHCH(R2)CO2C2H5 and CNCH2C(O)NHCH(R1)C(O)NHCH (R2)C(O)NHCH(R3)CO2CH3 (R1 = R2 = R3 = CH2C6H5, R2 = H, CH2C6H5) are available by condensation of potassium isocyanoacetate with amino acid esters or peptide esters. These isocyanides form with chloro‐bridged complexes [(arene)M(Cl)(μ‐Cl)]2 (arene = Cp*, p‐cymene, M = Ir, Rh, Ru) in the presence of Ag[BF4] or Ag[CF3SO3] the cationic halfsandwich complexes [(arene)M(isocyanide)3]+X? (X = BF4, CF3SO3). 相似文献
12.
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
13.
Ibaniewkor Lyngdoh Mawnai Sanjay Adhikari Lincoln Dkhar Jaya Lakshmi Tyagi Krishna Mohan Poluri 《Journal of Coordination Chemistry》2019,72(2):294-308
The reaction of [(arene)MCl2]2 with pyridylpyrazolyl ligands (L1 and L2) in the presence of ammonium hexafluorophosphate leads to formation of cationic complexes having the general formula [(arene)M(L)Cl]PF6 {M?=?Ru, arene = p-cymene (1, 4); Cp*, M?=?Rh (2, 5); Cp*, M?=?Ir (3, 6); L?=?2-(1H-pyrazol-1-yl)pyridine (L1), 2-(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (L2)}. Similarly the reaction of [CpRu(PPh3)2Cl] and [(ind)Ru(PPh3)2Cl] (ind?=?η5-C9H7) with L1 and L2 yielded cationic complexes which have been formulated as [(Cp/ind)Ru(L)PPh3]PF6 (7–10). All these complexes were characterized by analytical and spectroscopic techniques. The pyridylpyrazolyl ligands coordinated metal through pyridyl and pyrazolyl nitrogens forming a six-membered metallacycle. The ligands as well as the complexes were evaluated for their in vitro antibacterial activity by agar well diffusion method against two Gram negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and two Gram positive bacteria (Staphylococcus aureus and Bacillus thuriengiensis). Results show that the ligands and the complexes have significant antibacterial activity against Gram negative bacteria. 相似文献
14.
The reaction of [RhCl(η4‐Ph2R2C4CO)]2 (R=Ph, 2‐naphthyl) with the dimeric complexes [RuCl2(p‐cymene)]2 p‐cymene=1‐methyl‐4‐(1‐methylethyl)benzene, [RuCl2(1,3,5‐Et3C6H3)]2, [MCl2(Cp*)]2 (M=Rh, Ir; Cp*=1,2,3,4,5‐pentamethylcyclopenta‐2,4‐dien‐1‐yl), [RuCl2(CO)3]2, [RuCl2(dcypb)(CO)]2 (dcypb=butane‐1,4‐diylbis[dicyclohexylphosphine]), [(dppb)ClRu(μ‐Cl)2(μ‐OH2)RuCl(dppb)] (dppb=butane‐1,4‐diylbis[diphenylphosphine]), and [(dcypb)(N2)Ru(μ‐Cl)3RuCl(dcypb)] was investigated. In all cases, mixed, chloro‐bridged complexes were formed in quantitative yield (see 5 – 8, 9 – 16, 18, 19, 21 , and 22 ). The six new complexes 5, 8, 9, 13, 15 , and 22 were characterized by single‐crystal X‐ray analysis (Figs. 1–3). 相似文献
15.
Chiral Half‐sandwich Pentamethylcyclopentadienyl Rhodium(III) and Iridium(III) Complexes with Schiff Bases from Salicylaldehyde and α‐Amino Acid Esters [1] A series of diastereoisomeric half‐sandwich complexes with Schiff bases from salicylaldehyde and L‐α‐amino acid esters including chiral metal atoms, [(η5‐C5H5)(Cl)M(N,O‐Schiff base)], has been obtained from chloro bridged complexes [(η5‐C5Me5)(Cl)M(μ‐Cl)]2 (M = Rh, Ir). Abstraction of chloride from these complexes with Ag[BF4] or Ag[SO3CF3] affords the highly sensitive compounds [(η5‐C5Me5)M(N,O‐Schiff base]+X? (M = Rh, Ir; X = BF4, CF3SO3) to which PPh3 can be added under formation of [(η5‐C5Me5)M(PPh3)(N,O‐Schiff base)]+X?. The diastereoisomeric ratio of the complexes ( 1 ‐ 7 and 11 ‐ 12 ) has been determined from NMR spectra. 相似文献
16.
Dr. Natalia Busto Jesús Valladolid Cristina Aliende Prof. Félix A. Jalón Prof. Blanca R. Manzano Dr. Ana M. Rodríguez Prof. Jorge F. Gaspar Celia Martins Dr. Tarita Biver Dr. Gustavo Espino Prof. José María Leal Prof. Begoña García 《化学:亚洲杂志》2012,7(4):788-801
The reactions of two diaminotriazine ligands 2,4‐diamino‐6‐(2‐pyridyl)‐1,3,5‐triazine (2‐pydaT) and 6‐phenyl‐2,4‐diamino‐1,3,5‐triazine (PhdaT) with ruthenium–arene precursors led to a new family of ruthenium(II) compounds that were spectroscopically characterized. Four of the complexes were cationic, with the general formula [(η6‐arene)Ru(κ2‐N,N‐2‐pydaT)Cl]X (X=BF4, TsO; arene=p‐cymene: 1.BF4 , 1.TsO arene=benzene: 2.BF4 , 2.TsO ). The neutral cyclometalated complex [(η6‐p‐cymene)Ru(κ2‐C,N‐PhdaT*)Cl] ( 3 ) was also isolated. The structures of complexes 2.BF4 and 3.H2O were determined by X‐ray diffraction. Complex 1.BF4 underwent a partial reversible‐aquation process in water. UV/Vis and NMR spectroscopic measurements showed that the reaction was hindered by the addition of NaCl and was pH‐controlled in acidic solution. At pH 7.0 (sodium cacodylate) Ru–Cl complex 1.BF4 was the only species present in solution, even at low ionic strength. However, in alkaline medium (KOH), complex 1.BF4 underwent basic hydrolysis to afford a Ru–OH complex ( 5 ). Fluorimetric studies revealed that the interaction of complex 1.BF4 with DNA was not straightforward; instead, its main features were closely linked to ionic strength and to the [DNA]/complex ratio. The bifunctional complex 1.BF4 was capable of interacting concurrently through both its p‐cymene and 2‐pydaT groups. Cytotoxicity and genotoxicity studies showed that, contrary to the expected behavior, the complex species was biologically inactive; the formation of a Ru–OH complex could be responsible for such behavior. 相似文献
17.
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
18.
Chemistry of Diruthenium and Dirhodium Analogues of Pentaborane(9): Synthesis and Characterization of Metal N,S‐Heterocyclic Carbene and B‐Agostic Complexes 下载免费PDF全文
M. Sc. Dipak Kumar Roy M. Sc. Bijan Mondal M. Sc. R. S. Anju Prof. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3640-3648
Building upon our earlier results on the synthesis of electron‐precise transition‐metal–boron complexes, we continue to investigate the reactivity of pentaborane(9) and tetraborane(10) analogues of ruthenium and rhodium towards thiazolyl and oxazolyl ligands. Thus, mild thermolysis of nido‐[(Cp*RuH)2B3H7] ( 1 ) with 2‐mercaptobenzothiazole (2‐mbtz) and 2‐mercaptobenzoxazole (2‐mboz) led to the isolation of Cp*‐based (Cp*=η5‐C5Me5) borate complexes 5 a , b [Cp*RuBH3L] ( 5 a : L=C7H4NS2; 5 b : L=C7H4NOS)) and agostic complexes 7 a , b [Cp*RuBH2(L)2], ( 7 a : L=C7H4NS2; 7 b : L=C7H4NOS). In a similar fashion, a rhodium analogue of pentaborane(9), nido‐[(Cp*Rh)2B3H7] ( 2 ) yielded rhodaboratrane [Cp*RhBH(L)2], 10 (L=C7H4NS2). Interestingly, when the reaction was performed with an excess of 2‐mbtz, it led to the formation of the first structurally characterized N,S‐heterocyclic rhodium‐carbene complex [(Cp*Rh)(L2)(1‐benzothiazol‐2‐ylidene)] ( 11 ) (L=C7H4NS2). Furthermore, to evaluate the scope of this new route, we extended this chemistry towards the diruthenium analogue of tetraborane(10), arachno‐[(Cp*RuCO)2B2H6] ( 3 ), in which the metal center possesses different ancillary ligands. 相似文献
19.
Mustapha Aitali Larbi El Firdoussi Abdellah Karim Alejandro F. Barrero Miguel Quirs 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(9):1088-1089
The title compound, [(S)‐2‐(anilinomethyl)pyrrolidine‐N,N′]‐chloro(η6‐para‐cymene)ruthenium(II) chloride, [RuCl‐(C10H14)(C11H16N2)]Cl, has been synthesized by the reaction of [RuCl2(p‐cymene)]2 (p‐cymene is para‐isopropyltoluene) with (S)‐2‐(anilinomethyl)pyrrolidine in triethylamine/2‐propanol. The Ru atom is in a pseudo‐tetrahedral environment coordinated by a chloride ligand, the aromatic hydrocarbon is linked in a η6 manner and the amine is linked via its two N atoms. The chloride anion is involved in hydrogen bonding with the diamine moieties through N—H?Cl interactions, with N?Cl distances of 3.273 (4) and 3.352 (4) Å. 相似文献
20.
Iris de Krom Dr. Evgeny A. Pidko Dr. Martin Lutz Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7523-7531
RhIII and IrIII complexes based on the λ3‐P,N hybrid ligand 2‐(2′‐pyridyl)‐4,6‐diphenylphosphinine ( 1 ) react selectively at the P?C double bond to chiral coordination compounds of the type [( 1 H ? OH)Cp*MCl]Cl ( 2 , 3 ), which can be deprotonated with triethylamine to eliminate HCl. By using different bases, the pKa value of the P? OH group could be estimated. Whereas [( 1 H ? O)Cp*IrCl] ( 4 ) is formed quantitatively upon treatment with NEt3, the corresponding rhodium compound [( 1 H ? O)Cp*RhCl] ( 5 ) undergoes tautomerization upon formation of the λ5σ4‐phosphinine rhodium(III) complex [( 1? OH)Cp*RhCl] ( 6 ) as confirmed by single‐crystal X‐ray diffraction. Blocking the acidic P? OH functionality in 3 by introducing a P? OCH3 substituent leads directly to the λ5σ4‐phosphinine iridium(III) complex ( 8 ) upon elimination of HCl. These new transformations in the coordination environment of RhIII and IrIII provide an easy and general access to new transition‐metal complexes containing λ5σ4‐phosphinine ligands. 相似文献