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This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals, and pharmaceuticals.

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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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Treatment of [IrCl3(tht)3], where tht = tetrahydrothiophene, with two equiv. of phenyl diphenylphosphinite (pdpitH) gave [Ir(pdpitH)(pdpit)(tht)Cl2] (1), which on further reaction with 3-t-butyl-5-(2-pyridyl)-1,2,4-triazole (bptzH) and NaOAc using a one-pot reaction afforded [Ir(pdpit)2(bptz)] (2). In sharp contrast, the reaction of [IrCl3(tht)3], pdpitH, and bptzH in the presence of a stronger base, Na2CO3, afforded a phenyl phenylphosphonite (pppo)-containing Ir(iii) complex [Ir(pdpit)(pppo)(bptz)] (3) that reveals a strong PO-H-N inter-ligand hydrogen bond (H-bond), as evidenced by the single crystal X-ray structural analysis. For confirmation, addition of diazomethane to a diethylether solution of 3 led to the isolation of two methylated Ir(iii) isomeric complexes, i.e. [Ir(pdpit)(pppoMe)(bptz)] (4) and [Ir(pdpit)(pppo)(bptzMe)] (5), possessing either a PO-Me or N-Me bonding fragment, respectively. The absorption spectrum of 3 in CH2Cl2 resembles that of 4, implying the dominant PO-H character in solution. Despite the prevailing PO-H character both in the solid crystal and in solution, its corresponding emission resembles that of 5, leading us to propose a mechanism incorporating the excited-state inter-ligand proton transfer (ESILPT) from PO-H to N-H isomeric form via the pre-existing PO?H?N hydrogen bond. The thermodynamics of proton transfer tautomerism are discussed on the basis of absorption/emission spectroscopy in combination with computational approaches; additional support is given by the relationship between emission pattern versus the position of protons and methyl substituents. The results demonstrate for the first time a paradigm of excited-state proton transfer for the transition metal complexes in the triplet manifold. This journal is

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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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Rhodium-catalyzed hydroformylation and deuterioformylation with pyrrolyl-based phosphorus amidite ligands: Influence of electronic ligand properties

The influence of electronic ligand properties on the catalyst performance in the rhodium-catalyzed hydroformylation of alkenes was investigated. Two bidentate phosphorous amidite and phosphinite ligands were also synthesized. The results show that all linear rhodium-alkyl species eventually undergo carbon monoxide insertion leading to highly linear aldehydes.

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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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Phosphorus compounds

The present invention relates to new nitrogen-containing organophosphorus compounds having aryloxy substituents bonded to phosphorus in ester structures. STR1 WHERE R’ is aryl or alkyl-substituted aryl of 6 to 10 carbon atoms, R” is alkyl, alkenyl or aryl groups of 1 to 15 carbon atoms and substituted aryl forms where the substituent is fluorine, chlorine, bromine, nitro, cyano, hydroxyl, alkyloxy or mixtures of such substituents, and Z is CO, or CS. The phosphorus compounds have utility as fire retardants and as biologically active materials.

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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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New phosphine-based bidentate ligands, 2-Me-8-Ph2P(X)C9H8NH (3, X = O; 4, X = S) and N-R-2-Ph2P(X)C6H4NH (5, R = Et, X = O; 6, R = Me, X = S; 7, R = Et, X = S) were prepared via ortho-lithiation of 1,2,3,4-tetrahydroquinaldine (2-Me-C9H9NH) and aniline derivatives (N-R-C6H5NH). Reaction of the ortho-lithiated compounds with 0.5 equiv of PhP(OPh)2 afforded the bis(amido)-phosphine ligands (2-Me-C9H8NH-8-yl)2PPh (8) and (N-R-C6H4NH-2-yl)2PPh (9, R = Me; 10, R = Et). Using these ligands, [amido-phosphine oxide]Hf(CH2Ph)3, [amido-phosphine sulfide]Hf(CH2Ph)3, [bis(amido)-phosphine]MX2 (M = Hf, Zr; X = CH2Ph, Cl, Me), and [amido-phosphine-amine]MCl3 complexes were prepared. The molecular structures of [amido-phosphine sulfide]Hf(CH2Ph)3 (13) (prepared using 6), [bis(amido)-phosphine]ZrMe2 (22) (prepared using 8), and [amido-phosphine-amine]MCl3 (23, M = Hf; 24, M = Zr; prepared using 9) were confirmed by X-ray crystallography. Most of the prepared complexes exhibited negligible or low activity for ethylene/1-octene copolymerization. The [amido-phosphine sulfide]Hf(CH2Ph)3 complex (13) exhibited relatively high copolymerization activity (19 ¡Á 106 g/mol-Hf h); however, this activity was unsatisfactory compared to that of the related [amido-phosphine]Hf(CH2Ph)3 complexes (up to 48 ¡Á 106 g/mol-Hf h).

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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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Self-assembled heteroleptic chiral ligands, assymetric catalyst systems and methods

A method of synthesizing a heteroleptic, multiple metal-containing metallocyclic catalyst, particularly suited for asymmetric catalysis, comprising combining a plurality of plural functional group-containing, monodentate ligands of complementary chirality, said plural functional groups being tethered to each other by tethers in the presence of a scaffold-structural metal Ms or derivative thereof, wherein at least one functional group on each ligand combines to ligate Ms to form a bidentate, Ms centered ligand scaffold containing the remaining functional groups and combining said bidentate ligand scaffold with a catalytic metal Mc or derivative thereof whereby the remaining functional groups combine to ligate Mc, thereby forming said catalyst.

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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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Tuning the cytotoxicity of ruthenium(ii) para-cymene complexes by mono-substitution at a triphenylphosphine/phenoxydiphenylphosphine ligand

The new complexes [RuCl2(eta6-p-cymene)(kappaP-Ph2PR)] [R = 4-C6H4OSiMe2tBu, 1; R = 4-C6H4Br, 2; R = OC(O)CHCl2, 3; R = OPh, 4; R = O(2-C6H4SiMe2tBu), 5] and [Ru(C2O4)(eta6-p-cymene){kappaP-Ph2PO(2-C6H4(SiMe2tBu))}], 6, were obtained in 83-98% yield from Ru(ii) arene precursors by three different synthetic strategies. The unprecedented phosphine Ph2P(O(2-C6H4SiMe2tBu)) was synthesized in 86% yield from 2-C6H4Br(OSiMe2tBu) and Ph2PCl, via intramolecular oxygen to carbon 1,3 migration of the silyl group (retro-Brook rearrangement). All the complexes were fully characterized by analytical and spectroscopic methods, and by single crystal X-ray diffraction in the cases of 3, 4, 5 and 6. Complexes 1-6 and the model compounds [RuCl2(eta6-p-cymene)(kappaP-PPh3)] (Ru-PPh3) and [Ru(C2O4)(eta6-p-cymene)(kappaP-PPh3)] (Ru-PPh3-O) underwent slow degradation in chloroform solutions upon air contact; the mixed valence complex [(eta6-p-cymene)Ru(mu-Cl)3RuCl2(kappaP-PPh3)], 7, was isolated from a solution of Ru-PPh3 in CHCl3, and X-ray identified. The antiproliferative activity of 1-6 and Ru-PPh3, Ru-PPh3-O and [RuCl2(eta6-p-cymene)(kappaP-PTA)] (RAPTA-C) was assessed towards the triple-negative breast cancer cell line MDA-MB-231, the ovarian carcinoma cell line A2780 and human skin fibroblasts (HSF). Complexes 1, 2, 5 and 6 displayed IC50 values significantly lower than that of cisplatin, with 2 providing a more potent cytotoxic effect on MDA-MB-231 and A2780 cancer cells compared to the noncancerous cell line (HSF). The stability of all complexes in DMSO/water solution was elucidated by NMR and conductivity measurements, and in particular 35Cl NMR spectroscopy was helpful to check the possible chloride dissociation. The stability studies suggest that the cytotoxic activity in vitro of the compounds is mainly ascribable to Ru(ii) species still bound to the phosphorus ligand.

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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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Air- and water-stable Lewis acids: Synthesis and reactivity of P-trifluoromethyl electrophilic phosphonium cations

A new class of electrophilic phosphonium cations (EPCs) containing a -CF3 group attached to the phosphorus(v) center is readily accessible in high yields, via a scalable process. These species are stable to air, water, alcohol and strong Br¡ãnsted acid, even at raised temperatures. Thus, P-CF3 EPCs are more robust than previously reported EPCs containing P-X moieties (X = F, Cl, OR), and despite their reduced Lewis acidity they function as Lewis acid catalysts without requiring anhydrous reaction conditions.

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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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Cis-Dichloro Sulfoxide Ligated Ruthenium Metathesis Precatalysts

Novel sulfoxide-ligated ruthenium complexes were prepared by reacting second-generation metathesis precatalysts with p-toluenesulfonyl chloride in the presence of a small excess of sulfoxide. (SIMes)Ru(S-DMSO)(Ind)Cl2 (M54) and (SIMes)Ru(S-DMSO)(CHPh)Cl2 (M54a) were characterized crystallographically and, in agreement with NMR spectroscopy, were found to adopt an unusual cis-dichloro configuration. Despite having traditionally latent geometry, the new complexes were found to be highly reactive precatalysts for routine metathesis transformations. Additionally, the robustness, scalability, and industrial utility of M54 as a ruthenium synthon are demonstrated.

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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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Synthesis, characterization and dynamic behavior of some iridium carbonyl cluster complexes derived from Ir4(CO)12 with N-, P- and C-donor ligands: A survey

The synthesis of iridium dodecacarbonyl cluster derivatives Ir4(CO)12 with donor ligand such as amine, phosphites, hydrido and cyclic mono and dioxycarbene, NMR and X-ray characterization and fluxional behavior study in solution at variable temperature is briefly reviewed.

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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