Rhodium(I) Complexes with a η-Fluorenyl--phosphanylphosphorane Ligand.

The first example of a -phosphanylphosphorane, Flu═PCy-PCy (; Flu = 9-fluorenyl), has been easily prepared by P-phosphination of lithiated 9-dicyclohexylphosphinofluorene (FluPCy, ) with chlorodicyclohexylphosphane. constitutes a new type of P(III)-P(V) organophosphorus compound, a σλ-σλ species that is stable under an inert atmosphere in the solid state. The reaction of with [Rh(diene)]BR causes metalation of the benzylic carbon (C9) of fluorene, giving κ-C,P complexes in which fluorene is coordinated in the η form.

Cytotoxicity of osmium(II) and cycloosmated half-sandwich complexes from 1-pyrenyl-containing phosphane ligands.

Five metal-arene complexes of formula [MX(η--cymene)(diR(1-pyrenyl)phosphane)] (M = Os or Ru, X = Cl or I, R = isopropyl or phenyl) and symbolized as were synthesized and fully characterized, namely , , , and . Furthermore, nine cyclometalated half-sandwich complexes of formula [MX-(η--cymene)(C-diR(1-pyrenyl)phosphane)] (M = Os or Ru, X = Cl or I, R = isopropyl or phenyl) or [M(η--cymene)(S-dmso)(C-diR(1-pyrenyl)phosphane)]PF (M = Os or Ru, R = isopropyl or phenyl) and symbolized as were prepared; hence, , , , , , , , and were obtained and fully characterized. The crystal structures of ten out of the fourteen complexes were solved.

Magnetic and optical studies of a new family of multidimensional and multiproperty PO-lanthanide(III) derived systems.

A new family of lanthanide compounds has been synthesized using 1,2-bis(diphenylphosphino)ethane dioxide (dppeO) as an O-donor ligand through the phosphoryl group to lanthanide(III) cations and structurally, magnetically and optically studied. Depending on the lanthanide, two different topologies appear: the two-dimensional structure [Ln(dppeO)(NO)(HO)] (Ln = Ce (1), Sm (2) and Dy (6)) and the one-dimensional structure [Ln(dppeO)(NO)DMF] (Ln = Eu (3), Gd (4) and Tb (5)). Some of the Ln-derived complexes have been used as structural probes, while others have been synthesized to use the specific characteristics of each cation to take advantage of their magnetic/luminescence properties.

Rhodium and ruthenium complexes of methylene-bridged, -stereogenic, unsymmetrical diphosphanes.

Enantiopure -stereogenic methylphosphane-boranes ()-P(BH)PhArMe (; Ar = 1-naphthyl (NpMe), and 2-biphenylyl (BiphMe)) have been used to prepare diphosphanes of the type ArPhPCHPR (R = Ph, iPr or Bu; ). The ligands have been reacted with [Rh(COD)]BF to furnish the corresponding six monochelated [Rh(COD)()]BF organometallic compounds (RhArR) or, depending on the reaction conditions, the bis(chelated) coordination compound [Rh()]BF as a mixture of and isomers. The crystal structure of -[Rh()]BF was obtained.

Piano-Stool Ruthenium(II) Complexes with Delayed Cytotoxic Activity: Origin of the Lag Time.

We have recently reported a series of piano-stool ruthenium(II) complexes of the general formula [RuCl(η-arene)(P(1-pyrenyl)RR)] showing excellent cytotoxic activities (particularly when R = R = methyl). In the present study, new members of this family of compounds have been prepared with the objective to investigate the effect of the steric hindrance of a bulky phosphane ligand, namely diisopropyl(1-pyrenyl)phosphane (), on exchange reactions involving the coordinated halides (X = Cl, I). Two η-arene rings were used, i.

Access to α-Aminophosphonic Acid Derivatives and Phosphonopeptides by [Rh(P-OP)]-Catalyzed Stereoselective Hydrogenation.

The hydrogenation of -substituted vinylphosphonates using rhodium complexes derived from P-OP ligands , -, or as catalysts has been successfully accomplished, achieving very high levels of stereoselectivity (up to 99% ee or de). The described synthetic strategy allowed for the efficient preparation of α-aminophosphonic acid derivatives and phosphonopeptides, which are valuable building blocks for the preparation of biologically relevant molecules.

Direct Asymmetric Hydrogenation of N-Methyl and N-Alkyl Imines with an Ir(III)H Catalyst.

A novel cationic [IrH(THF)(P,N)(imine)] [BAr] catalyst containing a P-stereogenic MaxPHOX ligand is described for the direct asymmetric hydrogenation of N-methyl and N-alkyl imines. This is the first catalytic system to attain high enantioselectivity (up to 94% ee) in this type of transformation. The labile tetrahydrofuran ligand allows for effective activation and reactivity, even at low temperatures.

Highly Cytotoxic Ruthenium(II)-Arene Complexes from Bulky 1-Pyrenylphosphane Ligands.

In the present study, the potential anti-neoplastic properties of a series of ruthenium half-sandwich complexes of formula [Ru(η-arene)Cl(PRR(1-pyrenyl))] (η-arene = p-cymene and R = R = methyl for 1; η-arene = methylbenzoate and R = R = methyl for 2; η-arene = p-cymene and R = R = phenyl for 3; η-arene = methylbenzoate and R = R = phenyl for 4; η-arene = p-cymene, R = methyl and R = phenyl for 5; η-arene = methylbenzoate, R = methyl and R = phenyl for 6) have been investigated. The six structurally related organoruthenium(II) compounds have been prepared in good yields and fully characterized; the X-ray structures of three of them, i.e.

Growth of Au-PdSn Nanorods via Galvanic Replacement and Their Catalytic Performance on Hydrogenation and Sonogashira Coupling Reactions.

Colloidal PdSn and Au-PdSn nanorods (NRs) with tuned size were produced by the reduction of Pd and Sn salts in the presence of size- and shape-controlling agents and the posterior growth of Au tips through a galvanic replacement reaction. PdSn and Au-PdSn NRs exhibited high catalytic activity toward quasi-homogeneous hydrogenation of alkenes (styrene and 1-octene) and alkynes (phenylacetylene and 1-octyne) in dichloromethane. Au-PdSn NRs showed higher activity than PdSn for 1-octene, 1-octyne, and phenylacetylene.

Synthesis and coordination chemistry of enantiopure t-BuMeP(O)H.

Both enantiomers of the optically pure Secondary Phosphine Oxide (SPO) t-BuMeP(O)H (1) have been obtained by deboronation of phosphinous acid-borane t-BuMeP(O)H·BH3 (3) with HBF4 followed by hydrolysis of the intermediate adduct t-BuMeP(O)H·BF3 (1·BF3), which has been isolated and crystallographically characterised. Complexes [MCl(COD)(κP-(R)-1)] (M = Ir, Rh; 4 and 7 respectively) have been detected in solution but could not be isolated while trans-[RhCl(CO)(κP-(S)-1)2] (9) has been successfully obtained in good yield. Gold complex [AuCl(κP-(S)-1)] (10) has been prepared and its crystal structure shows the presence of aurophilic interactions.

Half-sandwich complexes of Ir(iii), Rh(iii) and Ru(ii) with the MaxPhos ligand: metal centred chirality and cyclometallation.

The reaction of the acetylacetonates [(η-CMe)M(acac)Cl] with (S)-[HMaxPhos][BF] afforded cationic complexes with the formula (S,R)-[(η-CMe)MCl(MaxPhos)][BF] (M = Rh (1), Ir (2)). The reaction of (S)-MaxPhos with [RuCl(μ-Cl)(η-p-MeCHPr)] and NHX afforded (S,R)-[(η-p-MeCHPr)RuCl(MaxPhos)][X] (X = BF (3), PF (3')). The complexes have been completely characterized by analytical and spectroscopic means, including the determination of the crystal structures of 1, 2 and 3'.

Ruthenium complexes of P-stereogenic phosphines with a heterocyclic substituent.

The synthesis via phosphine-boranes of 13 new optically pure P-stereogenic diarylphosphines P(Het)PhR (Het = 4-dibenzofuranyl (DBF), 4-dibenzothiophenyl (DBT), 4-dibenzothiophenyl-S,S-dioxide (DBTO2) and 1-thianthrenyl (TA); R = OMe, Me, i-Pr, Fc (ferrocenyl)) following the Jugé-Stephan method is described. The ligands were designed with the aim of having a heteroatom in a position capable of interacting with a metal upon coordination. The ligands and their precursors have been fully characterised, including the determination of two crystal structures of phosphine-boranes.

Borane as an efficient directing group. Stereoselective 1,2-addition of organometallic reagents to borane P-stereogenic N-phosphanylimines.

In non-coordinating solvents, borane was shown to be an efficient directing group for the stereoselective 1,2-addition of organolithium reagents to P-stereogenic N-phosphanylimines. Selectivity was reversed in coordinating solvents. This process can lead to novel ligand scaffolds for asymmetric catalysis.

Homoleptic ruthenium complex bearing dissymmetrical 4-carboxy-4'-pyrrolo-2,2'-bipyridine for efficient sensitization of TiO(2) in solar cells.

An easily accessible homoleptic complex [Ru(L3)(3)](2+) containing a dissymmetrical bipyridine (L3) substituted by a pyrrole and a carboxylic group has been evaluated in a dye-sensitized solar cell. The new dye displayed extended absorption domain, high absorbance, and a promising 65% IPCE value. Higher scores were reached using a cobalt-iron mediator instead of the usual LiI/I(2) couple for regeneration of the Ru(II) state.

Ruthenium complexes bearing pi-extended pyrrolo-styryl-bipyridine ligand: electronic properties and evaluation as photosensitizers.

A new Ru(L)(dcbpy)(NCS)2 dye containing a pyrrole-based pi-extended ligand has been prepared and showed very good light harvesting ability with near 70% IPCE in the visible region. The performance is very close to those of the standard N3 with a wider absorption range.