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In this study, the cytotoxic activities of structurally related cycloplatinated(ii) complexes containing chelating and bridging 1,1?-bis(diphenylphosphino)ferrocene (dppf) ligand derived from a wide range of C^N cyclometalating ligands (vpy = deprotonated 2-vinylpyridine, bzq = deprotonated benzo[h]quinoline, bpy = deprotonated 2,2?-bipyridine, bpyO = deprotonated 2,2?-bipyridine N-oxide, and ppy = deprotonated 2-phenylpyridine), were evaluated against human lung (A549), ovarian (SKOV3) and breast (MCF-7) cancer cell lines. The most cytotoxic compounds, 2a, 2c and 2d, effectively produced cell death by inducing apoptosis in the A549, SKOV3 and MCF-7 cancer cell lines. In addition, the molecular docking simulation was performed to determine the specific binding mode and the orientation of binding to DNA. According to the results of biological evaluation, the dppf-containing cycloplatinated(ii) complexes exhibited strong interactions with DNA as well as high cytotoxicity and apoptosis-inducing activities to human cancer cell line. The present study suggests that precise rational design of new platinum-based complexes would result in the preparation of potential anticancer drugs, which can induce facile apoptosis.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Five mono-nuclear silver (I) complexes with 6,7-dicyanodipyridoquinoxaline ligand, namely {[Ag(DPEphos)(dicnq)]NO3}2·CH3OH (1), [Ag(DPEphos)(dicnq)]BF4·CH3OH (2), [Ag(XANTphos)(dicnq)]CF3SO3 (3), {[Ag(XANTphos)(dicnq)]NO3}2 (4), and [Ag(XANTphos)(dicnq)]ClO4·CH2Cl2 (5) {DPEphos = bis[2-(diphenylphosphanyl)phenyl]ether, dicnq = 6,7-dicyanodipyridoquinoxaline, XANTphos = 9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene} were characterized by X-ray diffraction, IR, 1H NMR, 31P NMR, fluorescence spectra, and terahertz time-domain spectra (THz-TDS). In the five complexes the AgI, which is coordinated by two kinds of chelating ligands, adopts four-coordinate modes to generate mono-nuclear structures. The C?H···pi interactions lead to formation of a 1D infinite chain for complexes 2 and 3. The crystal packing of complexes 1 and 5 reveal that they form 3D supermolecular network by several pairs of C?H···pi interactions. The emissions of these complexes are attributed to ligands-centered [pi?pi*] transition based on both of the P-donor and N-donor ligands.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Hetero-trinuclear complexes of formula [(C6F5)2Pt(mu-PPh2)2M(dppf)] [dppf = 1,1?-bis(diphenylphosphino)ferrocene, M = Pt (1), M = Pd (2)] were prepared by coupling between cis-[(C6F5)2Pt(PPh2)2]Li2and cis-MCl2(dppf). Reaction of the Pt/Pt/Fe species 1 with [Ag(OClO3)(PPh3)] or I2resulted in the formation of the complexes [(C6F5)(PPh3)Pt(mu-PPh2)2Pt(dppf)] (3) and [(C6F5)(I)Pt(mu-PPh2)2Pt(dppf)] (4), respectively, in which one of the pentafluorophenyl ligands has been replaced by PPh3or I. Reaction of the Pt/Pd/Fe species 2 with Ag(ClO4) afforded the tetranuclear complex [(C6F5)2Pt(mu-PPh2)2Pd(dppf)Ag] (5) where the silver atom is bonded to Pd, to one of the bridging P and to one of the dppf P atoms. With [Ag(OClO3)(PPh3)], complex 5 is also formed, although mixed with [Ag(PPh3)2][ClO4]. A dynamic process in solution, in which the silver atom passes from one Pd?muPPh2bond to the other, has been observed at room temperature for complex 5. The crystal structures of 3, 4 and 5 are reported.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Transition metal-catalysed cross-coupling is one of the most powerful synthetic methods and has led to vast improvements in the synthesis of pharmaceuticals, agrochemicals and precursors for materials chemistry. A major advance in cross-coupling over the past 20 years is the utilization of well-defined, bench-stable Pd and Ni precatalysts that do not require the addition of free ancillary ligand, which can hinder catalysis by occupying open coordination sites on the metal. The development of precatalysts has resulted in new reactions and expanded substrate scopes, enabling transformations under milder conditions and with lower catalyst loadings. This Review highlights recent advances in the development of Pd and Ni precatalysts for cross-coupling, and provides a critical comparison between the state of the art in Pd- and Ni-based systems.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The palladium dibromide complexes of (S,R)-(1,1′-bis-diphenylphosphino)-2-ferrocenylethyldimethylamine and (S,R)-(1-diphenylphosphino)-2-ferrocenylethyldimethylamine have been reduced with dilithiocyclooctatetraene to form the corresponding Pd0 cyclooctatetraene complexes.Their reactions with E-4-methoxy-2′-bromophenylethene, and then benzylmagnesium chloride at -60 to -30 deg C, provide information on the structure of intermediates in asymmetric cross-coupling.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Two polymorphs of dinuclear mercury-iron complexes, [HgBr2(dppf)] (1) where dppf is 1,1′-bis (diphenylphosphino)ferrocene, are prepared and crystal structures are determined by X-ray crystallography. The reaction of mercury(II) bromide with dppf in methanol-dichloromethane led to orange block polymorph. After crystallization of this complex in DMSO, a red needle polymorph was obtained.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Compounds of Formula I and Formula II, pharmaceutically acceptable salt thereof, stereoisomers of any of the foregoing, or mixtures thereof are agonists of the APJ Receptor and may have use in treating cardiovascular and other conditions. Compounds of Formula I and Formula II have the structures where the definitions of the variables are provided herein.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A novel cuprous complex bearing two functional parts, i.e. a luminophoric part and a structural part, exhibits distinct luminescence responses to a variety of volatile organic compounds of different polarities in the solid state.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Reaction of Cp4Fe4(CO)4 (1) with RLi and HBF4 in sequence affords Cp3Fe4(CO)4(C5H4R) (R= Me, Bun, and Ph) in moderate yields. Further sequential PhLi/HBF4 treatment of Cp3Fe4(CO)4(C5H4Ph) produces Cp2Fe4(CO)4(C5H4Ph) 2. On the other hand, 1 reacts with lithium diisopropylamide (LDA) and bromoferrocene sequentially to produce a ferrocenylated cluster [Cp3Fe4(CO)4(C5H 4)][(C5H4)FeCp] (3) and a double cluster [Cp3Fe4(CO)4(C5H4)] 2 (2). A similar LDA/dibromoferrocene treatment with 1 leads to 2, [Cp3Fe4(CO)4(C5H 4)][(C5H4)(C5H4Br)Fe] (4), and a ferrocenyl-bridged double cluster [Cp3Fe4(CO)4(C5H4)] 2[(C5H4)2Fe] (5). The new compounds have been characterized by elemental analysis and IR, mass, and NMR spectroscopy.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Reaction of polymeric gold(I) acetylide species (bpyC?CAu) n (bpyC?CH = 5-ethynyl-2,2?-bipyridine) with diphosphine ligands Ph2P(CH2)nPPh2 (n = 2-6) or 1,1?-bis(diphenylphosphino)-ferrocene (dppf) in dichloromethane induces isolation of binuclear gold(I) complexes (bpyC?CAu)2{mu- Ph2P(CH2)nPPh2} or (bpyC?CAu)2(mu-dppf). Complexation of Ln(hfac)3 (hfac = hexafluoroacetylacetonate, Ln = Nd, Eu, Er, Yb) subunits to the binuclear gold(I) complexes through 2,2?-bipyridyl chelation gives the corresponding Au4Ln4 or Au2Ln2 heteropolynuclear complexes. Noticeably, upon formation of the Au 4Ln4 arrays by complexation of (bpyC?CAu) 2(mu-Ph2P(CH2)4PPh2) (3) with Ln(hfac)3 units, trans-conformation in 3 transforms dramatically to the cis-arranged form due to the strong driving force from ligand-unsupported Au-Au contacts between two Au2Ln2 subunits. In contrast, cis-conformation in (bpyC?CAu)2(mu- dppf) (6) stabilized by Au-Au interactions is reversed to the trans-oriented form upon formation of Au2Ln2 arrays by introducing Ln(hfac)3 units through 2,2-bipyridyl chelation. The binuclear gold(I) complexes show bright blue luminescence featured by ligand-centered pi ? pi* (C?Cbpy) states together with low-energy emission at 500-540 nm, associated with 3(pi?pi*) excited states, mixed probably with some characteristic from (Au-Au) ? (C?Cbpy) 3MMLCT transition. For Au4Ln4 or Au 2Ln2 complexes, sensitized lanthanide luminescence is achieved by energy transfer from Au-acetylide chromophores with lifetimes in the sub-millisecond range for EuIII complexes, whereas in the microsecond range for near-infrared emitting NdIII, ErIII, and YbIII species.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate