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1.
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
2.
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
3.
The mononuclear amidinate complexes [(η6‐cymene)‐RuCl( 1a )] ( 2 ) and [(η6‐C6H6)RuCl( 1b )] ( 3 ), with the trimethylsilyl‐ethinylamidinate ligands [Me3SiC≡CC(N‐c‐C6H11)2]– ( 1a– ) and[Me3SiC≡CC(N‐i‐C3H7)2]– ( 1b– ) were synthesized in high yields by salt metathesis. In addition, the related phosphane complexes[(η5‐C5H5)Ru(PPh3)( 1b )] ( 4a ) [(η5‐C5Me5)Ru(PPh3)( 1b )] ( 4b ), and [(η6‐C6H6)Ru(PPh3)( 1b )](BF4) ( 5 ‐BF4) were prepared by ligand exchange reactions. Investigations on the removal of the trimethyl‐silyl group using [Bu4N]F resulted in the isolation of [(η6‐C6H6)Ru(PPh3){(N‐i‐C3H7)2CC≡CH}](BF4) ( 6 ‐BF4) bearing a terminal alkynyl hydrogen atom, while 2 and 3 revealed to yield intricate reaction mixtures. Compounds 1a / b to 6 ‐BF4 were characterized by multinuclear NMR (1H, 13C, 31P) and IR spectroscopy and elemental analyses, including X‐ray diffraction analysis of 1b , 2 , and 3 . 相似文献
4.
Victoria A. Ternes Hannah A. Morgan Austin P. Lanquist Michael J. Murray Bradley M. Wile 《应用有机金属化学》2020,34(4):e5459
Herein we report the preparation of a series of Ru(II) complexes featuring α-iminopyridine ligands bearing thioether functionality (NNSR, where R = Me, CH2Ph, Ph). Metallation using [(p-cymene)RuCl]2 permits access to Ru complexes with a κ2-N,N donor set in which the thioether moiety remains uncoordinated. In the presence of a strong field ligand such as acetonitrile or triphenylphosphine, the p-cymene moiety is displaced, and the ligand adopts a κ3-N,N,S binding mode. These complexes are characterized using a combination of solution and solid state methods, including the crystal structure of [(NNSMe)Ru (NCMe)2Cl]Cl. The κ2-N,N-Ru(II) complexes are shown to serve as efficient precatalysts for the oxidation of sec-phenethyl alcohol at modest loadings (alcohol: Ru = 20:1), using a variety of external oxidants and solvents. The complex bearing an S-Ph donor was found to be the most active oxidation catalyst of those surveyed, suggesting that the thioether donor plays an active role in the catalytic cycle. 相似文献
5.
New water-soluble complexes [(η6-C6H6)RuCl(C5H4N-2-CH?=?N-R)]Cl (1) (with R?=?4-hydroxymethylphenyl (a), 2,4-dichlorophenyl (b), 2-fluorophenyl (c), 3-carboxyphenyl (d)) have been synthesized by reacting [(η6-C6H6)Ru(μ-Cl)Cl]2 with the N,N′-bidentate ligands in a 1:2 ratio. Full characterization of all complexes was accomplished using 1H and 13C NMR, elemental analyses, UV-Vis spectroscopy, IR spectroscopy and single crystal X-ray crystallography for determination of the structure of 1d, as 1d·4H2O. The single crystal structure confirmed coordination of the ligand to the ruthenium(II) center leading to a structure commonly described as a pseudo-octahedral, three-legged piano stool. The geometry around the Ru(II) center is such that the arene ring occupies the apex of the stool while the N,N′-bidentate ligand and a chloride occupy the base of the stool. The synthesized Ru(II) complexes were tested as catalysts for oxidation of styrene using NaIO4 as a co-oxidant in a biphasic system. All complexes were active, giving good yields of benzaldehyde. Catalyst 1c was later investigated for olefin oxidation and gave high yields of the corresponding aldehydes as the major products in all cases. 相似文献
6.
Pamela G. Alsabeh Dr. Rylan J. Lundgren Dr. Robert McDonald Dr. Carin C. C. Johansson Seechurn Dr. Thomas J. Colacot Prof. Dr. Mark Stradiotto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2131-2141
An examination of the [{Pd(cinnamyl)Cl}2]/Mor‐DalPhos (Mor‐DalPhos=di(1‐adamantyl)‐2‐morpholinophenylphosphine) catalyst system in Buchwald–Hartwig aminations employing ammonia was conducted to better understand the catalyst formation process and to guide the development of precatalysts for otherwise challenging room‐temperature ammonia monoarylations. The combination of [{Pd(cinnamyl)Cl}2] and Mor‐DalPhos afforded [(κ2‐P,N‐Mor‐DalPhos)Pd(η1‐cinnamyl)Cl] ( 2 ), which, in the presence of a base and chlorobenzene, generated [(κ2‐P,N‐Mor‐DalPhos)Pd(Ph)Cl] ( 1 a ). Halide abstraction from 1 a afforded [(κ3‐P,N,O‐Mor‐DalPhos)Pd(Ph)]OTf ( 5 ), bringing to light a potential stabilizing interaction that is offered by Mor‐DalPhos. An examination of [(κ2‐P,N‐Mor‐DalPhos)Pd(aryl)Cl] ( 1 b – f ) and related precatalysts for the coupling of ammonia and chlorobenzene at room temperature established the suitability of 1 a in such challenging applications. The scope of reactivity for the use of 1 a (5 mol %) encompassed a range of (hetero)aryl (pseudo)halides (X=Cl, Br, I, OTs) with diverse substituents (alkyl, aryl, ether, thioether, ketone, amine, fluoro, trifluoromethyl, and nitrile), including chemoselective arylations. 相似文献
7.
Sabina‐Alexandra Filimon Cristian G. Hrib Sören Randoll Ion Neda Peter G. Jones Matthias Tamm Prof. Dr. 《无机化学与普通化学杂志》2010,636(5):691-699
Two new optically active bidentate N,N‐ligands, DMIQCI ( 3a ) and DMIQCD ( 3b ), containing a quinuclidine core and an imidazolidin‐2‐imine unit, were synthesized. The reaction of these ligands with [(η5‐C5Me5)RuCl]4 afforded the brick‐red ruthenium(II) complexes [(η5‐C5Me5)Ru(DMIQCI)Cl] ( 4 ) and [(η5‐C5Me5)Ru(DMIQCD)Cl] ( 5 ), which were used as catalysts in the transfer hydrogenation of acetophenone in boiling 2‐propanol. The reactions of 3a and 3b with [(COD)PdCl2] (COD = 1,5‐cycloocta‐diene) and with [(DME)NiBr2] (DME = 1,2‐dimethoxyethane) afforded the square‐planar palladium(II) complexes [(DMIQCI)PdCl2] ( 7 ) and [(DMIQCD)PdCl2] ( 8 ) or the tetrahedral nickel(II) complexes [(DMIQCI)NiBr2] ( 9 ) and [(DMIQCD)NiBr2] ( 10 ), respectively. The X‐ray crystal structures of 4 , 7 , 9· THF, and 10 are reported. 相似文献
8.
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
9.
Kota Thirumala Prasad A.K. Chandra Kollipara Mohan Rao 《Journal of organometallic chemistry》2010,695(5):707-2022
Reactions of 3,6-bis(2-pyridyl)-4-phenylpyridazine (Lph) with [(η6-arene)Ru(μ-Cl)Cl]2 (arene = C6H6, p-iPrC6H4Me and C6Me6), [(η5-C5Me5)M(μ-Cl)Cl]2, (M = Rh and Ir) and [(η5-Cp)Ru(PPh3)2Cl] (Cp = C5H5, C5Me5 and C9H7) afford mononuclear complexes of the type [(η6-arene)Ru(Lph)Cl]PF6, [(η5-C5Me5)M(Lph)Cl]PF6 and [(Cp)Ru(Lph)(PPh3)]PF6 with different structural motifs depending on the π-acidity of the ligand, electronic properties of the central metal atom and nature of the co-ligands. Complexes [(η6-C6H6)Ru(Lph)Cl]PF61, [(η6-p-iPrC6H4Me)Ru(Lph)Cl]PF62, [(η5-C5Me5)Ir(Lph)Cl]PF65, [(η5-Cp)Ru(PPh3)(Lph)]PF6, (Cp = C5H5, 6; C5Me5, 7; C9H7, 8) show the type-A binding mode (see text), while complexes [(η6-C6Me6)Ru(Lph)Cl]PF63 and [(η5-C5Me5)Rh(Lph)Cl]PF64 show the type-B binding mode (see text). These differences reflect the more electron-rich character of the [(η6-C6Me6)Ru(μ-Cl)Cl]2 and [(η5-C5Me5)Rh(μ-Cl)Cl]2 complexes compared to the other starting precursor complexes. Binding modes of the ligand Lph are determined by 1H NMR spectroscopy, single-crystal X-ray analysis as well as evidence obtained from the solid-state structures and corroborated by density functional theory calculations. From the systems studied here, it is concluded that the electron density on the central metal atom of these complexes plays an important role in deciding the ligand binding sites. 相似文献
10.
The mononuclear cations of the general formula [(η6-arene)RuCl(dpqMe2)]+ (dpqMe2 = 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline; arene = C6H6, 1; C6H5Me, 2; p-PriC6H4Me, 3; C6Me6, 4) as well as the dinuclear dications [(η6-arene)2Ru2Cl2(μ-dpqMe2)]2+ (arene = C6H6, 5; C6H5Me, 6; p-PriC6H4Me, 7; C6Me6, 8) have been synthesised from 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline (dpqMe2) and the corresponding chloro complexes [(η6-C6H6)Ru(μ-Cl)Cl]2, [(η6-C6H5Me)Ru(μ-Cl)Cl]2, [(η6-p-PriC6H4Me)Ru(μ-Cl)Cl]2 and [(η6-C6Me6)Ru(μ-Cl)Cl]2, respectively. The X-ray crystal structure analyses of [1][PF6], [3][PF6] and [6][PF6]2 reveal a typical piano-stool geometry around the metal centre; in the dinuclear complexes the two chloro ligands, with respect to each other, are found to be trans oriented. 相似文献
11.
《Journal of Coordination Chemistry》2012,65(14):2523-2534
Dinuclear arene ruthenium complexes [(η6-arene)Ru(μ-Cl)Cl]2 (arene?=?C6H6; p iPrC6H4Me; C6Me6) and monomeric cyclopentadienyl complexes [(η5-Cp)Ru(PPh3)2Cl] (Cp?=?cyclopentadienyl) react with polypyridyl nitrogen ligands L1 (3-(pyridin-2-yl)-1H-1,2,4-triazole) and L2 (1,3-bis(di-2-pyridylaminomethyl)benzene) in methanol to afford cationic mononuclear compounds [(η6-arene)Ru(L1)Cl]+ (arene?=?C6H6, 1; p iPrC6H4Me, 2; C6Me6, 3), [(η6arene)Ru(L2)Cl]+ (arene?=?C6H6, 4; p iPrC6H4Me, 5; C6Me6, 6), [(η5-Cp)Ru(L1)(PPh3)]+ (7), and [(η5Cp)Ru(L2)(PPh3)]+ (8). All cationic mononuclear compounds were isolated as their hexafluorophosphate salts and characterized by elemental analyses, NMR, and IR spectroscopic methods and some representative complexes by UV-Vis spectroscopy. The solid state structures of two derivatives, [6]PF6 and [7]PF6, have been determined by the X-ray structure analysis. 相似文献
12.
Iris de Krom Leen E. E. Broeckx Dr. Martin Lutz Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3676-3684
The bidentate P,N hybrid ligand 1 allows access for the first time to novel cationic phosphinine‐based RhIII and IrIII complexes, broadening significantly the scope of low‐coordinate aromatic phosphorus heterocycles for potential applications. The coordination chemistry of 1 towards RhIII and IrIII was investigated and compared with the analogous 2,2′‐bipyridine derivative, 2‐(2′‐pyridyl)‐4,6‐diphenylpyridine ( 2 ), which showed significant differences. The molecular structures of [RhCl(Cp*)( 1 )]Cl and [IrCl(Cp*)( 1 )]Cl (Cp*=pentamethylcyclopentadienyl) were determined by means of X‐ray diffraction and confirm the mononuclear nature of the λ3‐phosphinine–RhIII and IrIII complexes. In contrast, a different reactivity and coordination behavior was found for the nitrogen analogue 2 , especially towards RhIII as a bimetallic ion pair [RhCl(Cp*)( 2 )]+[RhCl3(Cp*)]? is formed rather than a mononuclear coordination compound. [RhCl(Cp*)( 1 )]Cl and [IrCl(Cp*)( 1 )]Cl react with water regio‐ and diastereoselectively at the external P?C double bond, leading exclusively to the anti‐addition products [MCl(Cp*)( 1 H ? OH)]Cl as confirmed by X‐ray crystal‐structure determination. 相似文献
13.
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
14.
The ability of the tetraaza‐dithiophenolate ligand H2L2 (H2L2 = N,N′‐Bis‐[2‐thio‐3‐aminomethyl‐5‐tert‐butyl‐benzyl]propane‐1,3‐diamine) to form dinuclear chromium(III) complexes has been examined. Reaction of CrIICl2 with H2L2 in methanol in the presence of base followed by air‐oxidation afforded cis,cis‐[(L2)CrIII2(μ‐OH)(Cl)2]+ ( 1a ) and trans,trans‐[(L2)CrIII2(μ‐OH)(Cl)2]+ ( 1b ). Both compounds contain a confacial bioctahedral N2ClCrIII(μ‐SR)2(μ‐OH)CrIIIClN2 core. The isomers differ in the mutual orientation of the coligands and the conformation of the supporting ligand. In 1a both Cl? ligands are cis to the bridging OH function. In 1b they are in trans‐positions. Reaction of the hydroxo‐bridged complexes with HCl yielded the chloro‐bridged cations cis,cis‐[(L2)CrIII2(μ‐Cl)(Cl)2]+ ( 2a ) and trans,trans‐[(L2)CrIII2(μ‐Cl)(Cl)2]Cl ( 2b ), respectively. These bridge substitutions proceed with retention of the structures of the parent complexes 1a and 1b . 相似文献
15.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(2):489-498
The new compounds [(acac)2Ru(μ‐boptz)Ru(acac)2] ( 1 ), [(bpy)2Ru(μ‐boptz)Ru(bpy)2](ClO4)2 ( 2 ‐(ClO4)2), and [(pap)2Ru(μ‐boptz)Ru(pap)2](ClO4)2 ( 3 ‐(ClO4)2) were obtained from 3,6‐bis(2‐hydroxyphenyl)‐1,2,4,5‐tetrazine (H2boptz), the crystal structure analysis of which is reported. Compound 1 contains two antiferromagnetically coupled (J=?36.7 cm?1) RuIII centers. We have investigated the role of both the donor and acceptor functions containing the boptz2? bridging ligand in combination with the electronically different ancillary ligands (donating acac?, moderately π‐accepting bpy, and strongly π‐accepting pap; acac=acetylacetonate, bpy=2,2′‐bipyridine pap=2‐phenylazopyridine) by using cyclic voltammetry, spectroelectrochemistry and electron paramagnetic resonance (EPR) spectroscopy for several in situ accessible redox states. We found that metal–ligand–metal oxidation state combinations remain invariant to ancillary ligand change in some instances; however, three isoelectronic paramagnetic cores Ru(μ‐boptz)Ru showed remarkable differences. The excellent tolerance of the bpy co ‐ ligand for both RuIII and RuII is demonstrated by the adoption of the mixed ‐ valent form in [L2Ru(μ‐boptz)RuL2]3+, L=bpy, whereas the corresponding system with pap stabilizes the RuII states to yield a phenoxyl radical ligand and the compound with L=acac? contains two RuIII centers connected by a tetrazine radical‐anion bridge. 相似文献
16.
Emily J. Thompson Thomas W. Myers Louise A. Berben 《Angewandte Chemie (International ed. in English)》2014,53(51):14132-14134
The synthesis of two four‐coordinate and square planar (SP) complexes of aluminum(III) is presented. Reaction of a phenyl‐substituted bis(imino)pyridine ligand that is reduced by two electrons, Na2(PhI2P2?), with AlCl3 afforded five‐coordinate [(PhI2P2?)Al(THF)Cl] ( 1 ). Square‐planar [(PhI2P2?)AlCl] ( 2 ) was obtained by performing the same reaction in diethyl ether followed by lyphilization of 2 from benzene. The four‐coordinate geometry index for 2 , τ4, is 0.22, where 0 would be a perfectly square‐planar molecule. The analogous aluminum hydride complex, [(PhI2P2?)AlH] ( 3 ), is also square‐planar, and was characterized crystallographically and has τ4=0.13. Both 2 and 3 are Lewis acidic and bind 2,6‐lutidine. 相似文献
17.
Heterodinuclear Ruthenium(II) Complexes of the Bridging Ligand 1,6,7,12‐Tetraazaperylene with Iron(II), Cobalt(II), Nickel(II), as well as Palladium(II) and Platinum(II) 下载免费PDF全文
Thomas Brietzke Alexandra Kelling Uwe Schilde Wulfhard Mickler Hans‐Jürgen Holdt 《无机化学与普通化学杂志》2016,642(1):8-13
The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12‐tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N′‐dimethyl‐2,11‐diaza[3.3](2,6)‐pyridinophane (L‐N4Me2) ligand, yielding complexes of the general formula [(L‐N4Me2)Ru(µ‐tape)M(L‐N4Me2)](ClO4)2(PF6)2 with M = Fe {[ 2 ](ClO4)2(PF6)2}, Co {[ 3 ](ClO4)2(PF6)2}, and Ni {[ 4 ](ClO4)2(PF6)2}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)‐ and platinum(II)‐dichloride [(bpy)2Ru(μ‐tape)PdCl2](PF6)2 {[ 5 ](PF6)2} and [(dmbpy)2Ru(μ‐tape)PtCl2](PF6)2 {[ 6 ](PF6)2}, respectively were also prepared. The molecular structures of the complex cations [ 2 ]4+ and [ 4 ]4+ were discussed on the basis of the X‐ray structures of [ 2 ](ClO4)4 · MeCN and [ 4 ](ClO4)4 · MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono‐ and homodinuclear ruthenium(II) complexes of the tape bridging ligand. 相似文献
18.
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
19.
20.
Tuning the Electronic Properties in Ruthenium–Quinone Complexes through Metal Coordination and Substitution at the Bridge 下载免费PDF全文
Dr. Hari Sankar Das Dipl.‐Chem. David Schweinfurth Jan Fiedler Dr. Marat M. Khusniyarov Shaikh. M. Mobin Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(15):4334-4346
A rare example of a mononuclear complex [(bpy)2Ru(L1?H)](ClO4), 1 (ClO4) and dinuclear complexes [(bpy)2Ru(μ‐L1?2H)Ru(bpy)2](ClO4)2, 2 (ClO4)2, [(bpy)2Ru(μ‐L2?2H)Ru(bpy)2](ClO4)2, 3 (ClO4)2, and [(bpy)2Ru(μ‐L3?2H)Ru(bpy)2](ClO4)2, 4 (ClO4)2 (bpy=2,2′‐bipyridine, L1=2,5‐di‐(isopropyl‐amino)‐1,4‐benzoquinone, L2=2,5‐di‐(benzyl‐amino)‐1,4‐benzoquinone, and L3=2,5‐di‐[2,4,6‐(trimethyl)‐anilino]‐1,4‐benzoquinone) with the symmetrically substituted p‐quinone ligands, L, are reported. Bond‐length analysis within the potentially bridging ligands in both the mono‐ and dinuclear complexes shows a localization of bonds, and binding to the metal centers through a phenolate‐type “O?” and an immine/imminium‐type neutral “N” donor. For the mononuclear complex 1 (ClO4), this facilitates strong intermolecular hydrogen bonding and leads to the imminium‐type character of the noncoordinated nitrogen atom. The dinuclear complexes display two oxidation and several reduction steps in acetonitrile solutions. In contrast, the mononuclear complex 1 + exhibits just one oxidation and several reduction steps. The redox processes of 1 1+ are strongly dependent on the solvent. The one‐electron oxidized forms 2 3+, 3 3+, and 4 3+ of the dinuclear complexes exhibit strong absorptions in the NIR region. Weak NIR absorption bands are observed for the one‐electron reduced forms of all complexes. A combination of structural data, electrochemistry, UV/Vis/NIR/EPR spectroelectrochemistry, and DFT calculations is used to elucidate the electronic structures of the complexes. Our DFT results indicate that the electronic natures of the various redox states of the complexes in vacuum differ greatly from those in a solvent continuum. We show here the tuning possibilities that arise upon substituting [O] for the isoelectronic [NR] groups in such quinone ligands. 相似文献