Tetranuclear [Rh4(μ-PyS2) 2(diolefin)4] complexes as building blocks for new inorganic architectures: Synthesis of coordination polymers and heteropolynuclear complexes with electrophilic d8 and d10 metal fragments

The reaction of [Rh4(μ-PyS2)2(cod) 4] (PYS2 = 2,6-pyridinedithiolate, cod = 1,5-cyclooctadiene) with CF3SO3Me gave the cationic complex [Rh4(μ-PyS2Me)2(cod) 4][CF3SO3]2 (1) with two 6-(thiomethyl)pyridine-2-thiolate bridging ligands from the attack of Me+ at the terminal sulfur atoms of the starting material. Under identical conditions [Rh4(μ-PyS2)2(tfbb)4] (tfbb = tetrafluorobenzobarrelene) reacted with CF3SO3Me to give the mixed-ligand complex [Rh4(μ-PyS2)(μ-PyS 2Me)(tfbb)4][CF3SO3] (2). The nucleophilicity of the bridging ligands in the complexes [Rh4(μ -PyS2)2(diolefin)4] was exploited to prepare heteropolynuclear species. Reactions with [Au(PPh3)(Me 2CO)][ClO4] gave the hexanuclear complexes [(PPh 3)2Au2Rh4(μ-PyS2) 2(diolefin)4][ClO4]2 (diolefin = cod (3), tfbb (4)). The structure of 4, solved by X-ray diffraction methods, showed the coordination of the [Au(PPh3)]+ fragments to the peripheral sulfur atoms in [Rh4(μ-PyS2) 2(diolefin)4 along with their interaction with the neighbor rhodium atoms. Neutral coordination polymers of formula [CIMRh 4(μ-PyS2)2(diolefin)4] n (M = Cu (5, 6), Au (7)) result from the self-assembly of alternating [Rh4(μ-PyS2)2(diolefin) 4] ([Rh4]) blocks and MCI linkers. The formation of the infinite polymetallic chains was found to be chiroselective for M = Cu; one particular chain contains exclusively homochiral [Rh4] complexes. Cationic heterometallic coordination polymers of formula [MRh 4(μ-PyS2)2(diolefin)4] n (M = Ag (8, 9), Cu (10, 11)) and [Rh5(μ-PyS 2)2(diolefin)5]n[BF 4]n (12, 13) result from the reactions of [Rh 4] with [Cu(CH3CN)4]BF4, AgBF 4, and [Rh(diolefin)(Me2CO)2]BF4, respectively. The heterometallic coordination polymers exhibit a weak electric conductivity in the solid state in the range (1.2-2.8) × 10-7 S cm-1.The financial support from Ministerio de Ciencia y Tecnología (MCyT(DGI)/FEDER, Projects BQU2002-00074 and BQU2000-1170) is gratefully acknowledged.Peer Reviewe

Early (Ti, Zr)-late (Rh, Ir) heteronuclear complexes with bridging sulphido ligands

[EN]: We report in this account on the controlled synthesis of novel d0-d8 early-late heteropolynuclear diolefin and carbonyl clusters. The synthetic approach was based on additive-deprotonation reactions involving the titanium and zirconium bis-hydrosulphido complexes of formula [Cp2Ti(SH)2] and [Cptt 2Zr(SH)2] and appropriate rhodium and iridium diolefin and carbonyl compounds. The significant differences between the resulting early-late complexes and their structures coming from the titanium or zirconium metalloligand precursors are highlighted. The catalytic activity of some representative titanium-rhodium and zirconium-rhodium compounds towards alkene hydroformylation was explored. Interestingly, the heterotetranuclear 'CpTi(μ3-S)3Rh3' structure was maintained as such under mild conditions.[FR]: Nous rapportons dans cet article la préparation contrôlée de nouveaux clusters hétéropolynucléaires early-late d0–d8 portant les ligands oléfine et carbonyle. La réaction de déprotonation–addition a été la méthode de synthèse utilisée et implique la condensation de complexes bis-hydrogénosulfure du titane et du zirconium, de formule [Cp2Ti(SH)2] et [Cptt2Zr(SH)2], sur les composés adéquats du rhodium et de l’iridium portant les ligands oléfine et carbonyle. Les différences significatives de structure entre les complexes early-late ainsi préparés, dues à la nature du métalloligand précurseur du titane ou du zirconium employé, sont mises en évidence. L’activité catalytique de quelques composés représentatifs titane–rhodium et zirconium–rhodium dans l’hydroformylation d’alcènes a été mesurée. Il convient de noter que la structure hétérotétranucléaire « CpTi(μ3-S)3Rh3 » est maintenue comme telle sous des conditions douces de réaction.Peer Reviewe

Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds

The tetranuclear complexes [M4(μ-PyS2)2(diolefin)4] [PyS2 = 2,6-pyridinedithiolate; M = Rh, diolefin = cod (1,5-cyclooctadiene) (1), tfbb (tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene) (2); M = Ir, diolefin = cod (3), tfbb (4)] exhibit two one-electron oxidations at a platinum disk electrode in dichloromethane at potentials accessible by chemical reagents. The rhodium tetranuclear complexes were selectively oxidized to the monocationic complexes [Rh4(μ-PyS2)2(diolefin)4] + (1+, 2+) by mild one-electron oxidants such as [Cp2Fe]+ or [N(C6H4Br-4)3]+ and isolated as the PF6 -, BF4 -, and ClO4 - salts. Silver salts behave as noninnocent one-electron oxidants for the reactions with the rhodium complexes 1 and 2 since they give sparingly soluble coordination polymers. The complex [Ir4(μ-PyS2)2(cod)4] + (3+) was obtained as the tetrafluoroborate salt by reaction of 3 with 1 molar equiv of AgBF4, but the related complex 4+ could not be isolated from the chemical oxidation of [Ir4(μ-PyS2)2(tfbb)4] (4) with AgBF4. Oxidation of 3 and 4 with 2 molar equiv of common silver salts resulted in the fragmentation of the complexes to give the diamagnetic triiridium cations [Ir3(μ-PyS2)2(diolefin)3] +. The molecular structure of [Ir3(μ-PyS2)2(cod)3]BF 4, determined by X-ray diffraction methods, showed the three metal atoms within an angular arrangement. Both 2,6-pyridinedithiolate tridentate ligands bridge two metal-metal bonded d7 centers in pseudo octahedral environments and one d8 square-planar iridium center. An interpretation of the EPR spectra of the 63-electron mixed-valence paramagnetic tetranuclear complexes suggests that the unpaired electron is delocalized over two of the metal atoms in the complexes 1+-3+.The generous financial support from Dirección General de Enseñanza Superior e Investigación (DGES) (Projects PB98-641 and PB94-1186), and a fellowship (M. A. Casado) are gratefully acknowledged.Peer Reviewe

Iridium-Catalyzed Regio- and Diastereoselective Synthesis of C-Substituted Piperazines

Piperazine rings are essential motifs frequently found in commercial drugs. However, synthetic methodologies are mainly limited to N-substituted piperazines, preventing structural diversity. Disclosed herein is a straightforward catalytic method for the synthesis of complex C-substituted piperazines based on an uncommon head-to-head coupling of easily prepared imines. This 100% atom-economic process allows the selective formation of a sole diastereoisomer, a broad substrate scope, and a good functional group tolerance employing a bench-stable iridium catalyst under mild reaction conditions. Key to the success is the addition of N-oxides to the reaction mixture, as they notably enhance the catalytic activity and selectivity

Mixed-Valence Tetrametallic Iridium Chains

Neutral [X−{Ir2}−{Ir2}−X] (X=Cl, Br, SCN, I) and dicationic [L−{Ir2}−{Ir2}−L]2+ (L=MeCN, Me2CO) tetrametallic iridium chains made by connecting two dinuclear {Ir2} units ({Ir2}=[Ir2(μ‐OPy)2(CO)4], OPy=2‐pyridonate) by an iridium–iridium bond are described. The complexes exhibit fractional averaged oxidation states of +1.5 and electronic delocalization along the metallic chain. While the axial ligands do not significantly affect the metal–metal bond lengths, the metallic chain has a significant impact on the iridium–L/X bond distances. The complexes show free rotation around the unsupported iridium‐iridium bond in solution, with a low‐energy transition state for the chloride chain. The absorption spectra of these complexes show characteristic bands at 438–504 nm, which can be fine‐tuned by varying the terminal capping ligands

Synthesis, reactivity, and catalytic activity of triangular ZrM2 (M = Rh, Ir) early-late heterobimetallic complexes

Reactions of the zirconium−sulfide metallocene anion [Cptt2ZrS2]2- (Cptt = η5-1,3-di-tert-butylcyclopentadienyl) with [{M(μ-Cl)(diolefin)}2 gave the d0−d8 complexes [Cptt2Zr(μ3-S)2{M(diolefin)}2] (M = Rh, diolefin = 2,5-norbornadiene (nbd) (1), 1,5-cyclooctadiene (cod); M = Ir, diolefin = cod) with a triangular ZrM2 core capped by two symmetrical μ3-sulfido ligands. The rhodium complexes [Cptt2Zr(μ3-S)2{Rh(diolefin)}2] (diolefin = tetrafluorobenzobarrelene (tfbb), nbd, cod) can also be prepared by the additive-deprotonation reactions of the mononuclear [Rh(acac)(diolefin)] (diolefin = nbd, tfbb) and the dinuclear [{Rh(μ-OH)(cod)}2] complexes with [Cptt2Zr(SH)2]. These compounds exist as two rotamers in solution due to a hindered rotation of the cyclopentadienyl rings and the relative disposition of the substituents of the Cptt groups in the sandwich moiety. The reaction of [Cptt2Zr(SH)2] with [Ir(acac)(cod)] gave the complex [Cptt(acac)Zr(μ3-S)2{Ir(cod)}2] (5) with release of HCptt and coordination of acetylacetonate to the zirconium center. Carbonylation of compounds 1 and 5 yielded [Cptt2Zr(μ3-S)2{Rh(CO)2}2] (6) and [Cptt(acac)Zr(μ3-S)2{Ir(CO)2}2], respectively, while the complexes [Cptt2Zr(μ3-S)2{M(CO)2}2] (M = Rh, Ir) resulted also from the reaction of [Cptt2Zr(SH)2] with (PPh3Bz)[MCl2(CO)2] in the presence of triethylamine. Reactions of the carbonyl complexes with 1 molar equiv of bis(diphenylphosphino)methane (dppm) gave the cisoid complexes [Cptt2Zr(μ3-S)2{M(CO)}2(μ-dppm)] (M = Rh (9), Ir) with evolution of carbon monoxide. Monodentate phosphites, P(OMe)3 and P(OPh)3, react with 6 to give mixtures of the transoid and cisoid isomers [Cptt2Zr(μ3-S)2{Rh(CO)(P(OR)3)}2], which also exhibit a restricted rotation of the Cptt rings. The molecular structures of complexes 6 and 9 have been determined by X-ray diffraction methods. Compound 6 in the presence of P-donor ligands, P(OMe)3, P(OPh)3, and PPh3, is a precursor of the catalyst for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature. No Zr−Rh synergic effect is observed in this case, and the precursor breaks down after catalysis.We wish to thank Dirección General de Enseñanza Superior (DGES) and Diputación General de Aragón (DGA) for financial support (Projects PB88–0641 and P051/2000, respectively). Fellowships from the Ministerio de Educación y Cultura (M.A.F.H.-G.), Diputación General de Aragón (I.T.D.) and Programa CYTED (A.B.R.) are gratefully acknowledged.Peer Reviewe

Formas cuspidales de playas y procesos de la zona de rompientes interna: ¿crecimiento o destrucción? Aplicación a la playa de Trafalgar (Cádiz, España)

Large beach cusps (LBC, wavelength of ~ 30 m) are intertidal features that can alternately exist in the swash and in the inner surf zone due to tidal sea level changes. They have a larger cross-shore extent (up to 50 m) than traditional cusps. This extent has been explained by a shift of the swash zone during falling tide. The cusps immerse at rising tide and previous studies indicate that surf zone processes are exclusively destructive. Here, the behaviour of large beach cusps in the inner surf zone is investigated by using a 2DH morphological numerical model applied to Trafalgar Beach (Cádiz, Spain). The model results indicate that the inner surf zone processes do not always destroy the cusps but can in fact reinforce them by considering neither the swash processes nor the tidal changes. More generally, in conditions favouring the presence of the LBC the surf zone of a beach can be unstable, leading to the formation of transverse/oblique sand bars that can have characteristics similar to the LBC. Thus, in principle, the LBC could emerge not only due to swash zone morphodynamics but also due to surf zone morphodynamics or a combination of both.Las formas cuspidales de grandes dimensiones (LBC, longitudes de onda ~30 m) constituyen un sistema morfológico rítmico a lo largo de la playa que tiene una parte que se encuentra alternativamente en la zona de swash (flujo/reflujo) y en la zona de rompientes interna debido a los cambios del nivel del mar. Tienen una distancia de penetración de hasta 50 m, superior por tanto a la de las cúspides ordinarias. Esta elongación parece debido a la traslación de la zona de swash durante la marea descendente. En marea ascendente estas estructuras están sumergidas y los estudios previos consideran que los procesos de la zona de rompientes las destruyen. En este trabajo se analiza el comportamiento de estas formas en la zona de rompientes de la playa de Trafalgar (Cádiz) usando un modelo numérico morfológico 2DH. Los resultados muestran que, sin considerar ni los procesos de swash ni el cambio de marea, los procesos de la zona de rompientes no necesariamente destruyen LBC, sino que pueden reforzarlas. De forma más general, en condiciones favorables a la presencia de LBC, se pueden formar barras de arena con características similares a LBC debido a procesos de auto-organización en la zona de rompientes.The work of R. Garnier was supported by the University of Nottingham and is part of the Spanish Government project under contract CTM2006-08875. The Spanish Ministry of Science and Education (Project BORRASCAS CTM2005-06583) and the Junta de Andalucía (Projects P05-RNM-968 and P06-RNM-1573) funded part of this research

A user guide for the online exploration and visualization of PCAWG data.

Funder: U.S. Department of Health & Human Services | NIH | National Cancer Institute (NCI)Funder: Ontario Institute for Cancer Research (Institut Ontarien de Recherche sur le Cancer); doi: https://doi.org/10.13039/100012118Funder: EMBL Member States EU FP7 Programme projects EurocanPlatform (260791) CAGEKID (241669)Funder: European Union’s Framework Programme For Research and Innovation Horizon 2020 under the Marie Sklodowska-Curie grant agreement no. 703543Funder: Michael & Susan Dell Foundation; Mary K. Chapman Foundation; CCSG Grant P30 CA016672 (Bioinformatics Shared Resource); ITCR U24 CA199461; GDAN U24 CA210949; GDAN U24 CA210950Funder: European Commission's H2020 Programme, project SOUND, Grant Agreement no 633974Funder: Spanish Government (SEV 2015-0493) BSC-Lenovo Master Collaboration Agreement (2015)The Pan-Cancer Analysis of Whole Genomes (PCAWG) project generated a vast amount of whole-genome cancer sequencing resource data. Here, as part of the ICGC/TCGA Pan-Cancer Analysis of Whole Genomes (PCAWG) Consortium, which aggregated whole genome sequencing data from 2658 cancers across 38 tumor types, we provide a user's guide to the five publicly available online data exploration and visualization tools introduced in the PCAWG marker paper. These tools are ICGC Data Portal, UCSC Xena, Chromothripsis Explorer, Expression Atlas, and PCAWG-Scout. We detail use cases and analyses for each tool, show how they incorporate outside resources from the larger genomics ecosystem, and demonstrate how the tools can be used together to understand the biology of cancers more deeply. Together, the tools enable researchers to query the complex genomic PCAWG data dynamically and integrate external information, enabling and enhancing interpretation

Pan-cancer analysis of whole genomes identifies driver rearrangements promoted by LINE-1 retrotransposition

About half of all cancers have somatic integrations of retrotransposons. Here, to characterize their role in oncogenesis, we analyzed the patterns and mechanisms of somatic retrotransposition in 2,954 cancer genomes from 38 histological cancer subtypes within the framework of the Pan-Cancer Analysis of Whole Genomes (PCAWG) project. We identified 19,166 somatically acquired retrotransposition events, which affected 35% of samples and spanned a range of event types. Long interspersed nuclear element (LINE-1; L1 hereafter) insertions emerged as the first most frequent type of somatic structural variation in esophageal adenocarcinoma, and the second most frequent in head-and-neck and colorectal cancers. Aberrant L1 integrations can delete megabase-scale regions of a chromosome, which sometimes leads to the removal of tumor-suppressor genes, and can induce complex translocations and large-scale duplications. Somatic retrotranspositions can also initiate breakage–fusion–bridge cycles, leading to high-level amplification of oncogenes. These observations illuminate a relevant role of L1 retrotransposition in remodeling the cancer genome, with potential implications for the development of human tumors