Reactivity of Schiff base-[C,N,S] pincer palladacycles: hydrolysis renders singular trinuclear, tetranuclear, and heteropentanuclear Pd3W2 coordinated complexes.

Treatment of the Schiff base ligands a-f with Li2[PdCl4]/NaAcO in methanol under reflux gave the single nuclear palladacycles 1a-1f, with the metal atom bonded to a terdentate monoanionic [C,N,S] iminic ligand and to a chloride ligand that completes the palladium coordination sphere. Reaction of 1a-1c with silver perchlorate/triphenylphosphine in acetone at room temperature yielded the single nuclear complexes 2a-2c as the perchlorate salts, after substitution of the chloride ligand by a triphenylphosphine. However, reaction of a-c with Na2[PdCl4]/NaAcO in methanol at room temperature also gave compounds 1a-1c albeit contaminated with small amounts of the corresponding free aldehyde (mixture A). Reaction of mixture A with silver perchlorate/triphenylphosphine in acetone at room temperature gave analogously 2a-2c with some of the corresponding free aldehyde (mixture B). Attempts to purify mixtures A and B via recrystallization produced single crystals of 5 and 6 respectively: two serendipitously formed complexes, bearing thiomethyl aniline and/or acetate ligands, and void of aldehyde or iminic residue; the structures contain eight- and six-membered rings of alternating palladium and nitrogen atoms, respectively. To clarify this situation the aniline itself was reacted with palladium(II) acetate or with Na2[PdCl4]; in the latter case after recrystallization a unique behavior is revealed, giving rise to a tetranuclear complex containing a Pd4N4 ring with three differing coordination environments on the palladium atoms. Treatment of 1d with Ph2PCH2PPh2 (dppm)/AgClO4 or with Ph2PCH2(PPh2)W(CO)5/AgClO4 gave 3d, with a mono-coordinated dppm ligand, and 4d, respectively; complex 3d could not be converted into 4d by reaction with W(CO)5(THF). Recrystallization of 4d gave a still further noticeable species, complex 8: a pentanuclear trans-configured heterometallic mixed valent Pd(II)/W(0) linear complex with the palladium atoms supported by two acetate and two thiomethyl aniline bridging ligands. The complexes were fully characterized by microanalysis, IR, 1H, and 31P NMR spectroscopies, as appropriate. The X-ray single-crystal analyses for compounds 1b, 5, 6, 7 and 8 are described.

Cyclometallated Platinum(II) Complexes with Small Crown Ether Rings: Appropriate Choice of the Bridging Diphosphane to Coordinate Potassium Cations.

This account reports the synthesis and structural characterization of the first cyclometallated platinum(II) complex that coordinates a potassium cation in a sandwich arrangement via two 15-crown-5 ether rings within the same molecule. The cooperation of the two small crown ether moieties allows the entrapment of the non-ideal potassium ion. The reaction of the parent thiosemicarbazone ligand 3,4-(C8H16O5)C6H3C(Me)=NN-(H)C(=S)NHMe, 1, containing the crown ether ring, with K2[PtCl4], or alternatively with PtCl2(DMSO)2, and subsequent treatment with the diphosphanes Ph2PCH2PPh2 (dppm) and Ph2PC(=CH2)PPh2 (vdpp) produced the double nuclear platinacycles 3a, 3b, and 4, probably via formation of the 2a and 2b intermediates. Complex 3a with the K+ cation in a sandwich coordination was slightly mixed with 3b lacking any K+. Alternatively, reaction of 1 with K2[PtCl4] or with PtCl2(DMSO)2 followed by the diphosphane Ph2PC(=CH2)PPh2 (vdpp) only gave the dinuclear phosphane-bridged compound 4; this highlights the importance of choosing the right diphosphane ligand. Density functional theory calculations (B3LYP-D3/LANL2DZ-ECP-6.311++G**) revealed similar affinities for both dppm and vdpp derivatives to coordinate potassium cations. Crystal structure analysis was performed for compounds 3a and 4.

In Vitro and In Vivo Effect of Palladacycles: Targeting A2780 Ovarian Carcinoma Cells and Modulation of Angiogenesis.

Palladacycles are versatile organometallic compounds that show potential for therapeutic use. Here are described the synthesis and characterization of mono- and dinuclear palladacycles bearing diphosphines. Their biological effect was investigated in A2780, an ovarian-derived cancer line, and in normal dermal fibroblasts. The compounds displayed selective cytotoxicity toward the A2780 cell line. Compound 3 decreased the cell viability through cell cycle retention in G0/G1, triggered apoptosis through the intrinsic pathway, and induced autophagy in A2780 cells. Compound 9 also induced cell cycle retention, apoptosis, and cellular detachment. Notably, compound 9 induced the production of intracellular reactive oxygen species (ROS). Our work demonstrated that compound 3 enters A2780 cells via active transport, which requires energy, while compound 9 enters A2780 cells mostly passively. The potential effect of palladacycles in angiogenesis was investigated for the first time in an in vivo chorioallantoic membrane model, showing that while compound 3 displayed an antiangiogenic effect crucial to fighting cancer progression, compound 9 promoted angiogenesis. These results show that palladacycles may be used in different clinical applications where pro- or antiangiogenic effects may be desirable.

Chemistry of Tetradentate [C,N : C,N] Iminophosphorane Palladacycles: Preparation, Reactivity and Theoretical Calculations.

A theoretical and experimental study of tetradentate [C,N : C,N] iminophosphorane palladacycles was carried out for the purpose of elucidating their behavior as compared to the parent Schiff base analogues to determine the prospect of encountering new A-frame structures for the iminophosphorane derivatives. The DFT calculations were in agreement with the experimental results regarding the performance of these ligands. New insights into the chemistry of the related dinuclear species have been obtained.

From Chemical Serendipity to Translational Chemistry: New Findings in the Reactivity of Palladacycles.

In the world of science, in particular the section concerning the field of chemistry, when the results encountered during the experiment do not meet our expectations, our shrewdness may play an important role to open up new unexplored fields that could be much more interesting than what we were seeking. In those cases, our research undergoes an unforeseen shift, delivering novel and challenging results that may altogether alter our point of view and our future work. We have then struck serendipity. Specifically, in our investigation linked to palladacycles we have found that the new trends in their reactivity, as well as in their structure, have been, in many cases, related to this experience, broadening our research scope within this field. Herein, we describe our most relevant findings, which have shed new light upon the reactivity of palladacycles, thus opening new routes that lead to novel unexpected structures.

Palladium iminophosphorane complexes: the pre-cursors to the missing link in triphenylphosphane chalcogenide metallacycles.

Herein we report on the synthesis, characterization and the ensuing chemistry of iminophosphorane palladacycles. Treatment of Ph3P[double bond, length as m-dash]N-(2-OHC6H4), 1, with sodium tetrachloropalladate gives 2 with the ligand as terdentate [C,N,O] allowing for only one µ-Cl ligand bonding the metal centers, resulting in a dinuclear complex. Treatment of 2 with PPh3 gives the mononuclear complex 3, whereas the reaction of 2 with diphosphanes Ph2P(CH2)nPPh2 in 1 : 2 ratio gives mixtures of 4 and 5 (n = 2) and 6 and 7 (n = 3). From them, the mononuclear complexes 4 and 6, and the dinuclear compounds, 5 and 7, were obtained with the parent ligand as bidentate [C,N]. The former two are of zwitterionic nature void of any counterion, with the phosphane ligand in the chelating mode. In a remarkable case of chemical serendipity, a solution of 2 left to stand produced crystals of complex 8: this is the missing link in the series of triphenylphosphane chalcogenide metallacycles. The experiment is repeatable; however, direct metallation of triphenylphosphane oxide was not possible.

The chelate-to-bridging shift of phosphane dipalladacycles: convenient synthesis of double A-frame tetranuclear complexes.

Palladacycles of the type [Pd2(Ph2PCH2PPh2-P,P)2(C,N:C,N)] (C,N:C,N = bis(N-2,3,4-trimethoxybenzylidene)-4,4'-sulfonyldianiline or -4,4'-oxydianiline) can undergo a spontaneous slow chelate-to-bridging diphosphane coordination shift in solution. Following this strategy a tailor-made synthetic procedure was devised that culminates in isolation of double A-frame tetranuclear palladium complexes.

A Highly Effective Strategy for Encapsulating Potassium Cations in Small Crown Ether Rings on a Dinuclear Palladium Complex.

The potential of 15-crown-5 ethers to link large cations, such as potassium, is limited by the quasi-parallel arrangement of two oxygen donor moieties upon appropriate orientation of the corresponding ether-ring-containing molecules. Substrates bearing the two crown ethers that are capable of achieving such coordination are hitherto unknown. The synthesis and isolation of a tailor-made dinuclear palladacycle bearing 15-crown-5 ether rings on the metallated phenyls offers such a possibility, providing the adequate environment for the formation of the sandwiched [K(metallacycle-15-crown-5)2 ] moiety. This synthetic strategy also culminates in the isolation of the first palladacycle able to entrap a potassium cation through bonding to two 15-crown-5 ether rings in a single molecule.

Palladacycle catalysis: an innovation to the Suzuki-Miyaura cross-coupling reaction.

Herein we report a Suzuki-Miyaura type cross-coupling between an aryl halide and a functionalized boronic acid palladacycle in the absence of an external catalyst. This reaction is an unprecedented case of catalysis in palladium metallacycle chemistry.

Epidemiología de las lesiones del ligamento cruzado anterior en el futbolista profesional / Epidemiology of anterior cruciate ligament injuries in professional football players

La rotura del ligamento cruzado anterior (LCA) es una importante lesión ya que necesita de tratamiento quirúrgico y aleja al futbolista del campo por un periodo mínimo de 3-4 meses. Presentamos dos casuísticas realizadas sobre jugadores de fútbol en el ámbito profesional, con la intención de contribuir a clarificar algunos aspectos de la epidemiología de las lesiones del LCA en el futbolista. En la primera casuística, los ocho equipos de fútbol europeos tenían un total de 504 jugadores durante el periodo estudiado. En las cinco temporadas (1995-96 al 1999-2000) cada equipo ha tenido como media 69ñ7 jugadores diferentes. Los datos confirman que la mayor parte de las lesiones de la rodilla en el jugador de fútbol corresponden a lesiones del LCA y del ligamento lateral interno (LLI).La incidencia media del fútbol profesional masculino es de 6 lesiones del LCA por cada 100 jugadores en un periodo de cinco años. Las lesiones del LCA se producen prevalentemente por trauma indirecto (67 por ciento). La distribución de las lesiones parece ser independiente de la función en el campo, aunque exista una mener incidencia en los guardametas (2 por ciento). Los jugadores lesionados siguen un tratamiento quirúrgico que actualmente presenta preferencia por la reparación con tendón rotuliano autólogo (56 por ciento) con respecto al semitendinoso y grácil autólogo (44 por ciento). Existe una tendencia al aumento de las intervenciones quirúrgicas de reconstrucción con semitendinoso y grácil efectuado en las últimas dos temporadas en el 53 por ciento de los casos. Esta tendencia es clara en los equipos italianos, mientras en los otros equipos los casos estudiados son demasiado pocos como para definirlo como una tendencia. Los jugadores operados regresan al campo de juego como media después de 6,1 ñ 2,2 meses, con un rango de tiempo bastante amplio (3-14 meses) que depende probablemente de la presencia de lesiones asociadas o de la aparición complicaciones (AU)