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The carborane-selenol [(B10H11C2)SeH] has been isolated and its anion employed as a ligand. Reaction of the ligand with [AuClL] (L = PPh3, AsPh3) (1 : 1 molar ratio) or PPN[AuCl2] (PPN = N(PPh3)2) (2 : 1 molar ratio) affords the mononuclear compounds [Au(SeC2 B10H11)L] or PPN[Au(SeC2B10H11)2], respectively. Dinuclear derivatives [Au2(SeC2B10 H11)2(mu-PP)] (PP = 1,1?-bis(diphenylphosphino) ferrocene (dppf), 1,2-bis(diphenylphosphino)ethane (dppe)) are synthesised by reaction of the ligand with [Au2Cl2(mu-PP)] or by reaction of [Au(SeC2B10H11)-(AsPh3)] with the bidentate ligand. The selenolate acts in a bridging mode in [M2(mu-SeC2B10H11) (PPh3)2]X2 (M = Au, X = ClO4; M = Ag, X = TfO), obtained by treatment of the ligand with [O{Au(PPh3)}3]ClO4 or by reaction with [Ag(TfO)(PPh3)] in 1 : 2 molar ratio, respectively. The crystal structure of [Au(SeC2B10H11)(PPh3)] has been determined by X-ray diffraction studies.

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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 series of new heterometallic gold(I) thiolates containing ferrocenyl-phoshines were synthesized. Their antimicrobial properties were studied and compared to that of FDA-approved drug, auranofin (Ridaura), prescribed for the treatment of rheumatoid arthritis. MIC in the order of one digit micromolar were found for most of the compounds against Gram-positive bacteria Staphylococcus aureus and CA MRSA strains US300 and US400. Remarkably, auranofin inhibited S. aureus, US300 and US400 in the order of 150-300 nM. This is the first time that the potent inhibitory effect of auranofin on MRSA strains has been described. The effects of a selected heterometallic compound and auranofin were also studied in a non-tumorigenic human embryonic kidney cell line (HEK-293).

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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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Ph3PNCl (1) originates in good yield as pale yellow crystals from the reaction of Ph3PNSiMe3 with phenyliodine dichloride. According to the crystal structure analysis 1 has a monomeric molecular structure without perceptible intermolecular contacts with distances P-N of 161.0 pm, N-Cl of 175.9 pm, and with a PNCl bond angle of 110.31. 1 reacts with phosphines PR3 forming asymmetric PNP salts [Ph3PNPR3]Cl. This was tested by reactions with PEt3 and bis-diphenyl phosphano ferrocene (DPPF). The crystal structure analysis of [Ph3PNPEt3]Cl (2) shows an almost symmetric PNP bridge with distances PN of 158.6 and 157.0 pm, and with a bond angle of 145.9.

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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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An efficient approach to chloro(organophosphine) gold(i) complexes for the synthesis of auranofin

A practical and efficient synthesis of chloro(organophosphine) gold(i) complexes is reported. Employment of 4,4?-dihydroxydiphenyl sulfide as a safe and non-irritating reductant is highlighted for the generation of Au(i)-S intermediates, which could be trapped by mono- and bidentate phosphine ligands to provide organophosphine gold(i) complexes. The utility of the present method is further demonstrated by the synthesis of the antiarthritic drug auranofin.

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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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Synthetic and structural studies on transition metal fullerene complexes containing phosphorus and arsenic ligands (see abstract)

The reactions of C60 or C70 with M(PPh3)4 (M = Pt, Pd) in toluene or chlorobenzene at room temperature followed by in situ treatment of the intermediates (eta2-C60)M(PPh3)2 (1, M = Pt; 2, M = Pd) or (eta2-C70)M(PPh3)2 (3, M = Pt; 4, M = Pd) with dppf produced the corresponding bimetallic fullerene complexes (eta2-C60)M(dppf) (5, M = Pt; 6, M = Pd) and (eta2-C70)M(dppf) (7, M = Pt; 8, M = Pd). In addition, the reaction of C60 or C70 with Pt(AsPh3)4 and the reaction of C60 or C70 with Pt(dba)2 (dba = dibenzylideneacetone) and AsPh3 in toluene at room temperature both afforded the AsPh3-containing fullerene complexes (eta2-C60)Pt-(AsPh3)2 (9) and (eta2-C70)Pt(AsPh3)2 (10), whereas both the reaction of the isolated 9 or 10 with diarsine ligand dpaf and the reaction of Pt(AsPh3)4 with C60 or C70 followed by in situ treatment of the intermediates 9 and 10 with dpaf in toluene at room temperature yielded the dpaf-containing bimetallic fullerene complexes (eta2-C60)Pt(dpaf) (11) and (eta2-C70)Pt(dpaf) (12).

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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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Comparison of electrochemical behavior of exohedral palladium complexes with [60]- and [70]-fullerenes and metallocene ligands

Electronic structures of exohedral palladium complexes of [60]- and [70]-fullerenes with diphenylphosphinoferrocenyl, diphenylphosphinoruthenocenyl, and diphenylphosphinocymantrenyl ligands were studied by cyclic voltammetry and semiempirical quantum-chemical calculations. Probable sites of localization of electronic changes in the molecules of these complexes under electrochemical oxidation and reduction were determined.

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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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Abstract: Reaction of Na2[PdCl4] with two equivalents of 4,5-benzo-3H-1,2-dithiole-3-thione (btt) affords cis-[PdCl2(kappa1-btt)2] (1), which provides a convenient entry into mixed-ligand btt complexes. Addition of one equivalent of a range of diamines or diphosphines gives the salts [Pd(kappa1-btt)2(kappa2-diamine)]Cl2 (2a?d) (diamine = en, dap, bipy, phen) and [Pd(btt)2(kappa2-diphosphine)]Cl2 (3a?c) (diphosphine = dppe, dppp, dppf) in good yields. In contrast, two equivalents of dppm result in [Pd(kappa1-btt)2(kappa1-dppm)2]Cl2 (4), where the diphosphine binds in a monodentate fashion. Two equivalents of PPh3 result in a mixture of cis- and trans-isomers of [Pd(kappa1-btt)2(PPh3)2]Cl2 (5a?b) (ca. 1:5 ratio); the pure trans-isomer 5b was isolated by ion-exchange chromatography. The cis-isomer 5a could be synthesized independently from the reaction of cis-[PdCl2(PPh3)2] with two equivalents of btt. In all of these complexes, the btt ligand binds in a monodentate manner through the exocyclic thione sulfur. The anti-tumor activities of representative examples, cis-[PdCl2(kappa1-btt)2] (1), cis-[Pd(kappa1-btt)2(kappa1-dppm)2]Cl2 (4) and cis-[Pd(kappa1-btt)2(PPh3)2] (5a), were evaluated by cell proliferation assays and phase-contrast microscopy against prostate cancer cell lines PC3, DU145 and LNCaP, with complexes 1 and 4 showing potent anti-proliferative effects (TGI values of 19.2 and 21.1?mug/mL, respectively) against LnCaP cells. Graphical abstract: [Figure not available: see fulltext.].

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Reference£º
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 range of ruthenium-arene compounds with chloride, bromide or iodide ligands were prepared and tested as catalysts for the homogeneous redox neutral alkylation of tert-butylamine with phenethyl alcohol, and compared to the previously reported catalyst [RuCl2(p-cymene)]2, in the presence of the diphosphine 1,1?-bis(diphenylphosphino)ferrocene (dppf). The best catalytic activities were obtained with ruthenium iodide compounds. The formation of either [RuX(p-cymene)(dppf)][X] or [(RuX2(p-cymene)) 2(dppf)] (X = halide) under the catalytic conditions employed was investigated. Copyright

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Reference£º
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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[PPh4]2[M(C2N2 S2)2] (M = Pt, Pd) and [Pt(C2N2S2) (PR3)2] (PR3 = PMe2Ph, PPh3) and [Pt(C2N2S2)(PP)] (PP = dppe, dppm, dppf) were all obtained by the reaction of the appropriate metal halide containing complex with potassium cyanodithioimidocarbonate. The dimeric cyanodithioimidocarbonate complexes [{Pt(C2N2S2) (PR3)}2] (PR3 = PMe2Ph), [M{(C2N2 S2)(eta5-C5Me5)}2] (M = Rh, Ir) and [{Ru(C2N2S2) (eta6-p-MeC6H41Pr)}2] have been synthesised from the appropriate transition metal dimer starting material. The cyanodithioimidocarbonate ligand is S,S and bidentate in the monomeric complexes with the terminal CN group being approximately coplanar with the CS2 group and trigonal at nitrogen thus reducing the planar symmetry of the ligand. In the dimeric compound one of the sulfur atoms bridges two metal atoms with the core exhibiting a cubane-like geometry.

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Reference£º
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 series of diiron oxadithiolate model complexes for the active site of [Fe]-only hydrogenases Fe2(mu-SCH2OCH 2S-mu)(CO)6 (1), [Fe2(mu-SCH 2OCH2S-mu)-(CN)2(CO)4](Et 4N)2(2),[Fe2(muSCH2OCH 2S-mu)(CN)(CO)5}(Et4N) (3), Fe2(mu-SCH 2OCH2S-mu)(CO)5[CpFe(CO)2(SPh)] (4), and [Fe2(mu-SCH2OCH2S-mu) (CO) 5]2 [(eta 5-Ph2PC 2H4)2 Fe] (5) have been synthesized and fully characterized by elemental analysis, spectroscopy, and X-ray diffraction analysis. The structural features for some of the model complexes are compared with the corresponding features for the active site of[Fe]-only hydrogenases.

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Reference£º
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