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A multidentate and flexible diolefin-diphosphine ligand, based on the dibenzylidene acetone core, namely dbaphos (1), is reported herein. The ligand adopts an array of different geometries at Pt, Pd and Rh. At PtII the dbaphos ligand forms cis- and trans-diphosphine complexes and can be defined as a wide-angle spanning ligand. 1H NMR spectroscopic analysis shows that the beta-hydrogen of one olefin moiety interacts with the PtII centre (an anagostic interaction), which is supported by DFT calculations. At Pd0 and RhI, the dbaphos ligand exhibits both olefin and phosphine interactions with the metal centres. The Pd0 complex of dbaphos is dinuclear, with bridging diphosphines. The complex exhibits the coordination of one olefin moiety, which is in dynamic exchange (intramolecular) with the other “free” olefin. The Pd0 complex of dbaphos reacts with iodobenzene to afford trans-[PdII(dbaphos)I(Ph)]. In the case of RhI, dbaphos coordinates to form a structure in which the phosphine and olefin moieties occupy both axial and equatorial sites, which stands in contrast to a related bidentate olefin, phosphine ligand (“Lei” ligand), in which the olefins occupy the equatorial sites and phosphines the axial sites, exclusively. Copyright

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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 parallel synthesis of chiral bidentate ligands and their subsequent use in situ for a catalytic process is described. The ligands thus prepared gave comparable results to those obtained when the ligands were synthesized and purified by conventional means. This includes oxazolines and other compounds of similar complexity, meaning that for the first time these valuable compounds have been brought into the field of combinatorial catalysis.

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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 cobalt(III) complex with the condensation derivative of 2-(diphenylphosphino)benzaldehyde and ethyl carbazate was synthesized. X-ray crystal structure was determined for both the ligand and the complex. In the cobalt(III) complex two deprotonated ligand molecules coordinate the metal atom in a distorted octahedral geometry by chelation through the PNO donor system formed by the phosphorus, the imine nitrogen and the carbonyl oxygen. The complex showed a moderate antibacterial activity and a strong cytotoxic activity, stronger than cisplatin. Based on cell cycle progression, apoptotic assays, spectroscopic and electrophoretic studies, it was shown that high cytotoxicity and moderate potential of induction of apoptosis are not consequence of interactions with DNA.

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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 the cyclometallated compounds [Pd{2,3,4-(MeO)3C6HC(H){double bond, long}N[2-(O)-5-RC6H3]}]4 (1a: R = H, 1b: R = tBu) with the phosphine PPh2[2-(COH)C6H4], in a complex/phosphine 1:4 molar ratio gave the mononuclear cyclometallated complexes [{Pd{2,3,4-(MeO)3C6HC(H){double bond, long}N[2-(O)-5-RC6H3}}{PPh2[2-(HOC)C6H4]}] (2a: R = H; 2b: R = tBu), upon cleavage of the tetranuclear structure. Treatment of complex 1a with the diarsine AsPh2(CH2)2Ph2As (dppae) in a 1:2 or 1:4 molar ratio only yielded the dinuclear compound [{Pd{2,3,4-(MeO)3C6HC(H){double bond, long}N[2-(O)C6H4]}}2{mu-AsPh2(CH2)2Ph2As}] (3a), regardless the molar ratio used. Reaction of the cyclometallated tetramers with Ph2P(CH2)2Ph2As (arphos) in a 1:4 molar ratio gave the mononuclear cyclometallated complexes [Pd{2,3,4-(MeO)3C6HC(H){double bond, long}N[2-(O)C6H4]}{PPh2(CH2)2Ph2As-P}] (4a) and [Pd{2,3,4-(MeO)3C6HC(H){double bond, long}N[2-(O)-5-tBuC6H3]}{PPh2(CH2)2Ph2As-P}] (4b), with the P, As ligand coordinated through the phosphorus atom, as air-stable solids. Treatment of 1a with arphos in a 1:2 molar ratio gave the dinuclear complex [{Pd{2,3,4-(MeO)3C6HC(H){double bond, long}N[2-(O)C6H4]}}2{mu-PPh2(CH2)2Ph2As}] (5a). Reaction of 1b with the diphosphine Ph2P(C6H4)O(C6H4)PPh2 gave the dinuclear compound [{Pd{2,3,4-(MeO)3C6HC(H){double bond, long}N[2-(O)-tBuC6H3]}}2{mu-PPh2(C6H4)O(C6H4)Ph2P}] (6b) for all the complex 1b/phosphine molar ratios tested. Reaction of the cyclometallated tetramer 1a with PPh2[4-(NMe2)C6H4] (in 1:2 or 1:4 molar ratio) produced the mononuclear cyclometallated complex [Pd{2,3,4-(MeO)3C6HC(H){double bond, long}N[2-(O)C6H4]}{PPh2[4-(NMe2)C6H4]}] (7a) as an air-stable solid.

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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 self-assembly of [2]rotaxane has been achieved in aqueous media at pD 4 by the simultaneous threading into CB[7] of an appropriate axle ended with acyl hydrazine groups and its concurrent capping with two molecules of a triphenylphosphonium aldehyde as stoppers. The dynamism of the rotaxane has been demonstrated under acidic conditions and can be diminished by solvent swapping, pH modulation, or, surprisingly, the removal of the carbonyl groups on the axle.

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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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In the aspect of more effective ruthenium based catalyst design, three new ruthenium(II) phosphino-hydrazone/thiosemicarbazone complexes (1?3) have been synthesized by the reactions of cis-[RuCl2(dmso)4] or [RuHCl(CO)(AsPh3)3] with deprotonated 2-(2-(diphenylphosphino)benzylidene)-2-thiophenecarboxylic acid hydrazone (PNO-Thy) or 2-(2-(diphenylphosphino)benzylidene)-4-phenyl-3-thiosemicarbazone (PNS-Ph). The structures of the complexes (2 and 3) were established by X-ray crystallography and spectroscopic methods including elemental analysis, FT-IR and NMR (1H, 13C & 31P). Single crystal XRD upshots of complexes (2 and 3) revealed a distorted octahedral geometry around the ruthenium ion with hydrazone/thiosemicarbazone acts as a monoanionic tridentate PNO/PNS donor fashion. The catalytic study of complexes 1?3 towards regioselective N-alkylation reactions of amines was completed, showing that all catalysts are active toward catalytic transformations. Notably, complex 3 was found to be very efficient catalysts toward N-alkylation of a wide range of heterocyclic amines with alcohols. This catalysis provides a clean, convenient and practical route for the direct N-alkyl amine synthesis.

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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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Multidentate phosphines were readily obtained by reaction of chiral multidentate amines, prepared via ring opening of (S)-N-tosyl-2- isopropylaziridine with ammonia, primary, and secondary amines, with achiral phosphorus containing building blocks. The phosphines were used in palladium-catalyzed alkylation of rac-3-cyclohexenyl and cyclopentenyl carbonates. The enantioselectivity and reactivity were largely dependent on the structure of the amine core of the ligands. Up to 88% ee was observed in reactions with the six-membered substrate. The Royal Society of Chemistry 2006.

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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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Hydroformylation in homogeneous and heterogeneous systems, and hydroformylation related reactions of carbon monoxide reported in 2002 are reviewed.

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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 nickel(II) complexes ligated by the N-(1-(2-(diarylphosphino) phenyl)methylidene)quinolin-8-amines (P?N?N) and 2-(diphenylphosphino)- N-[2-(diarylphosphino)benzylidene]anilines (P?N?P) were synthesized and characterized by elemental analysis, spectroscopy, and X-ray crystallography. X-ray crystallographic analyses reveal complexes 16 and 20 as having a five-coordinated distorted trigonal-bipyramidal geometry, while complex 12 displays a distorted square-pyramidal geometry and complex 13 is distorted square planar. Upon activation with MAO and AlEtCl2, these complexes exhibited considerably high activity (up to 1.34 × 106 g·mol-1(Ni)·h-1) of ethylene oligomerization. It was found that ligand environment and reaction conditions significantly affect the activity of the catalysts. In addition, a cobalt analogue with a distorted tetrahedral coordination geometry was investigated, which showed low activity of ethylene oligomerization.

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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 new synthetic approach allows the synthesis of taniaphos- analogous ligands 2 with inverted alpha configuration (Sp, alphaS). This new class of ferrocenyl ligands displays excellent enantioselectivity and enhanced reactivity in several types of asymmetric hydrogenation reactions (e.g. 1?).

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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