Synthesis, Isolation and Characterization of a Triiodo Organometallic Palladium(IV) Complex. Quantitative and Regioselective Synthesis of Two C–I Reductive Elimination Products

©2011. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted version of a Published Work that appeared in final form in Inorganic Chemistry. To access the final edited and published work see https://doi.org/10.1021/ic2006869Iodine and the pincer complex [Pd(O,N,C-L)I], where L is the monoanionic ligand resulting from deprotonation of the acetyl group of the dimethylmonoketal of 2,6-diacetylpyridine, are in equilibrium at low temperatures with the Pd(IV) complex [Pd(O,N,C-L)I3], which can be isolated at –40 ºC and characterized by 1H NMR spectroscopy and Xray diffraction studies, in spite of its great instability. When the same reaction is carried out at room temperature, a quantitative reductive elimination process occurs giving L–I, which in the presence of water affords L'–I, resulting from hydrolysis of L–I

Synthesis of Bis-(2,6-dinitroaryl)palladium(II) and Mono-(2,6- dinitroaryl)platinum(II) Complexes. A New Example of the Transphobia Effect and of Transmetallation from Pt to Hg

©2008. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted version of a Published Work that appeared in final form in American Chemical Society. To access the final edited and published work see https://doi.org/10.1021/om701077yThe reaction of [Pd(k2-Ar)(O,O-acac)] (k2-Ar = k2-C,O-C6(NO2)2-2,6-(OMe); 1) with one equiv of RNC gives [Pd(k2-Ar)(O,O-acac)(CNR)] [R = Xy (2a), tBu (2b)] and with four equiv of XyNC, trans-[Pd(k1-Ar)2(CNXy)2] (k1-Ar = k1-C,O-C6(NO2)2-2,6-(OMe); 3). These complexes has also been obtained (1) by reacting Tl(acac) with one equiv of trans-[Pd(k1Ar)Cl(CNXy)2] (4), obtained in turn by reacting trans-(NMe4)2[Pd(k1-Ar)Cl(µ-Cl)]2 (5) with four equiv of XyNC or (2) by reacting [Pd(k1-Ar)(C-acac)(phen)] (6) with four equiv of XyNC. cis-[Pt(k2-Ar)(k1-Ar)(PPh3)] (7) reacts (1) with Hg(OAc)2 (1:1) to afford a mixture of [Hg(Ar)(OAc)], cis-[{Pt(k1-Ar)(PPh3)}2(µ-OH)(µ-OAc)] (8) and trans-[{Pt(k1-Ar)(PPh3)}2(µOH)2] (9) or (2) with HgCl2 (1:1) to give trans-[{Pt(k1-Ar)(PPh3)}2(µ-Cl)2] (10), which reacts with excess of Ag(OAc) to give 8. The reaction of 10 with excess of KOH, or with Tl(acac) (1:1) gives 9. Reaction of palladium complex 5 with two equiv of Hg(OAc)2 affords trans[Pd(k2-Ar)(µ-OAc)]2 (11). The crystal structures of 2a, 2b, 3, 5, 8, 9, and 11 have been determined

Organometallic Complexes of Palladium(II) Derived from 2,6- Diacetylpyridine Dimethylketal

©2010. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted version of a Published Work that appeared in final form in Organometallics. To access the final edited and published work see https://doi.org/10.1021/om100079xPdCl2 reacts with 2,6-diacetylpyridine (dap) (1 : 1) in refluxing MeOH to give the pincer complex [Pd(O1,N1,C1-L)Cl] (1) and (QH)2[PdCl2(-Cl)}]2 (2), where L is the monoanionic ligand resulting from the deprotonation of the acetyl methyl group of the monoketal of dap and QH is C5H3NHC(OMe)2Me2-2,6, the diketal of Hdap+. Reaction of 2 with NEt3 (1:2) in MeOH affords the diketal of dap, Q = C5H3NC(OMe)2Me}2-2,6 (3). Complex 1 reacts with two equiv of RNC at 0 ºC to give trans-[Pd(C1-L)Cl(CNR)2] (R = Xy (4a), tBu (4b)) but at room temperature affords [Pd(O2,C2-LR)Cl(CNR)] (R = Xy (5a), tBu (5b)). The ligand LR results from the insertion of one isocyanide into the Pd–C bond plus a tautomerization process from ketoimine to -ketoenamine, and coordinates in 5 through the carbonyl oxygen atom (O2) and the inserted isocyanide carbon atom (C2). The reaction of 1 with one equiv of RNC at 0 ºC leads a mixture of [Pd(N1,C1-L)Cl(CNR)] (R = Xy (6a), tBu (6b); 8590%), 1 and 4, but at room temperature gives the pincer complex [Pd(O1,N1,C2-LR)Cl] (R = Xy (7a), tBu (7b)) resulting from the same insertion/tautomerization processes that lead to 5. Complex 7 reacts at 0 ºC (1) with 2 equiv of RNC to give trans-[Pd(C2LR)Cl(CNXy)2] (R = Xy (8a), tBu (8b)) or (2) with one equiv of tBuNC to afford 5b. The reaction of 1 (1) with [Tl(acac)] gives [Pd(N1,C1-L)(acac)] (9), (2) with chelating ligands L^L affords [Pd(C1-L)Cl(N^N)] (N^N = 2,2’-bipyridine = bpy (10), 4,4’-di-tertbutyl-2,2’-bipyridine = dbbpy (11)), (3) with one equiv of PPh3 gives, in the same way as with isocyanides, an equilibrium mixture of [Pd(N1,C1-L)Cl(PPh3)] (12), 1 and trans[Pd(C1-L)Cl(PPh3)2] (13), which is the only product when two equiv of PPh3 is added to the reaction mixture, and (4) with excess of PPh3 affords the monoketal of dap, C5H3NC(O)Me-2}C(OMe)2Me-6} (14) and [Pd(PPh3)4]. The crystal structures of complexes 1, 2, 5b, 6a and 7a have been determined

Ru-Catalyzed C-H Arylation of Fluoroarenes with Aryl Halides

We gratefully acknowledge the Engineering and Physical Sciences Research Council (EPSRC, EP/I038578/1 and EP/ K039547/1) for funding and the European Research Council for a Starting Grant (to I.L.).

doi.org/10.1371/journal. pone.0250796

The aim was to analyze the characteristics and predictors of unfavorable outcomes in solid organ transplant recipients (SOTRs) with COVID-19. We conducted a prospective observational cohort study of 210 consecutive SOTRs hospitalized with COVID-19 in 12 Spanish centers from 21 February to 6 May 2020. Data pertaining to demographics, chronic underlying diseases, transplantation features, clinical, therapeutics, and complications were collected. The primary endpoint was a composite of intensive care unit (ICU) admission and/or death. Logistic regression analyses were performed to identify the factors associated with these unfavorable outcomes. Males accounted for 148 (70.5%) patients, the median age was 63 years, and 189 (90.0%) patients had pneumonia. Common symptoms were fever, cough, gastrointestinal disturbances, and dyspnea. The most used antiviral or host-targeted therapies included hydroxychloroquine 193/200 (96.5%), lopinavir/ritonavir 91/200 (45.5%), and tocilizumab 49/200 (24.5%). Thirty-seven (17.6%) patients required ICU admission, 12 (5.7%) suffered graft dysfunction, and 45 (21.4%) died. A shorter interval between transplantation and COVID-19 diagnosis had a negative impact on clinical prognosis. Four baseline features were identified as independent predictors of intensive care need or death: advanced age, high respiratory rate, lymphopenia, and elevated level of lactate dehydrogenase. In summary, this study presents comprehensive information on characteristics and complications of COVID-19 in hospitalized SOTRs and provides indicators available upon hospital admission for the identification of SOTRs at risk of critical disease or death, underlining the need for stringent preventative measures in the early post-transplant periodThis study was supported by Plan Nacional de I+D+i 2013-2016 and Instituto de Salud Carlos III, Subdirección General de Redes y Centros de Investigación Cooperativa, Ministerio de Ciencia, Innovación y Universidades, Spanish Network for Research in Infectious Diseases (REIPI RD16/0016); co-financed by European Development Regional Fund “A way to achieve Europe”, Operative Program Intelligence Growth 2014-2020. EC and JSC received grants from the Instituto de Salud Carlos III, Ministerio de Ciencia e Innovación, Proyectos de Investigación sobre el SARSCoV-2 y la enfermedad COVID-19 (COV20/ 00370; COV20/00580). JSC is a researcher belonging to the program “Nicola´s Monardes”(C0059–2018), Servicio Andaluz de Salud, Junta de Andalucía, Spain. SS-A is supported by a grant from the Instituto de Salud Carlos III, Ministerio de Ciencia e Innovación, Proyectos de Investigación sobre el SARS-Co

Risk factors for unfavorable outcome and impact of early post-transplant infection in solid organ recipients with COVID-19: A prospective multicenter cohort study

The aim was to analyze the characteristics and predictors of unfavorable outcomes in solid organ transplant recipients (SOTRs) with COVID-19. We conducted a prospective observational cohort study of 210 consecutive SOTRs hospitalized with COVID-19 in 12 Spanish centers from 21 February to 6 May 2020. Data pertaining to demographics, chronic underlying diseases, transplantation features, clinical, therapeutics, and complications were collected. The primary endpoint was a composite of intensive care unit (ICU) admission and/or death. Logistic regression analyses were performed to identify the factors associated with these unfavorable outcomes. Males accounted for 148 (70.5%) patients, the median age was 63 years, and 189 (90.0%) patients had pneumonia. Common symptoms were fever, cough, gastrointestinal disturbances, and dyspnea. The most used antiviral or host-targeted therapies included hydroxychloroquine 193/200 (96.5%), lopinavir/ritonavir 91/200 (45.5%), and tocilizumab 49/200 (24.5%). Thirty-seven (17.6%) patients required ICU admission, 12 (5.7%) suffered graft dysfunction, and 45 (21.4%) died. A shorter interval between transplantation and COVID-19 diagnosis had a negative impact on clinical prognosis. Four baseline features were identified as independent predictors of intensive care need or death: advanced age, high respiratory rate, lymphopenia, and elevated level of lactate dehydrogenase. In summary, this study presents comprehensive information on characteristics and complications of COVID-19 in hospitalized SOTRs and provides indicators available upon hospital admission for the identification of SOTRs at risk of critical disease or death, underlining the need for stringent preventative measures in the early post-transplant period

Association of Functional Polymorphisms of KIR3DL1/DS1 With Behçet's Disease

Behçet's disease (BD) is an immune-mediated vasculitis related to imbalances between the innate and adaptive immune response. Infectious agents or environmental factors may trigger the disease in genetically predisposed individuals. HLA-B51 is the genetic factor stronger associated with the disease, although the bases of this association remain elusive. NK cells have also been implicated in the etiopathogenesis of BD. A family of NK receptors, Killer-cell Immunoglobulin-like Receptor (KIR), with a very complex organization, is very important in the education and control of the NK cells by the union to their ligands, most of them, HLA class I molecules. This study aimed to investigate the contribution of certain KIR functional polymorphisms to the susceptibility to BD. A total of 466 BD patients and 444 healthy individuals were genotyped in HLA class I (A, B, and C). The set of KIR genes and the functional variants of KIR3DL1/DS1 and KIR2DS4 were also determined. Frequency of KIR3DL1004 was lower in patients than in controls (0.15 vs. 0.20, P = 0.005, Pc = 0.015; OR = 0.70; 95% CI 0.54-0.90) in both B51 positive and negative individuals. KIR3DL1004, which encodes a misfolded protein, is included in a common telomeric haplotype with only one functional KIR gene, KIR3DL2. Both, KIR3DL1 and KIR3DL2 sense pathogen-associated molecular patterns but they have different capacities to eliminate them. The education of the NK cells depending on the HLA, the balance of KIR3DL1/KIR3DL2 licensed NK cells and the different capacities of these receptors to eliminate pathogens could be involved in the etiopathogenesis of BD

Spatiotemporal Characteristics of the Largest HIV-1 CRF02_AG Outbreak in Spain: Evidence for Onward Transmissions

Background and Aim: The circulating recombinant form 02_AG (CRF02_AG) is the predominant clade among the human immunodeficiency virus type-1 (HIV-1) non-Bs with a prevalence of 5.97% (95% Confidence Interval-CI: 5.41–6.57%) across Spain. Our aim was to estimate the levels of regional clustering for CRF02_AG and the spatiotemporal characteristics of the largest CRF02_AG subepidemic in Spain.Methods: We studied 396 CRF02_AG sequences obtained from HIV-1 diagnosed patients during 2000–2014 from 10 autonomous communities of Spain. Phylogenetic analysis was performed on the 391 CRF02_AG sequences along with all globally sampled CRF02_AG sequences (N = 3,302) as references. Phylodynamic and phylogeographic analysis was performed to the largest CRF02_AG monophyletic cluster by a Bayesian method in BEAST v1.8.0 and by reconstructing ancestral states using the criterion of parsimony in Mesquite v3.4, respectively.Results: The HIV-1 CRF02_AG prevalence differed across Spanish autonomous communities we sampled from (p < 0.001). Phylogenetic analysis revealed that 52.7% of the CRF02_AG sequences formed 56 monophyletic clusters, with a range of 2–79 sequences. The CRF02_AG regional dispersal differed across Spain (p = 0.003), as suggested by monophyletic clustering. For the largest monophyletic cluster (subepidemic) (N = 79), 49.4% of the clustered sequences originated from Madrid, while most sequences (51.9%) had been obtained from men having sex with men (MSM). Molecular clock analysis suggested that the origin (tMRCA) of the CRF02_AG subepidemic was in 2002 (median estimate; 95% Highest Posterior Density-HPD interval: 1999–2004). Additionally, we found significant clustering within the CRF02_AG subepidemic according to the ethnic origin.Conclusion: CRF02_AG has been introduced as a result of multiple introductions in Spain, following regional dispersal in several cases. We showed that CRF02_AG transmissions were mostly due to regional dispersal in Spain. The hot-spot for the largest CRF02_AG regional subepidemic in Spain was in Madrid associated with MSM transmission risk group. The existence of subepidemics suggest that several spillovers occurred from Madrid to other areas. CRF02_AG sequences from Hispanics were clustered in a separate subclade suggesting no linkage between the local and Hispanic subepidemics

Complejos de Pd(II) y Pd(IV) derivados de la 2,6-diacetilpiridina: aplicaciones catalíticas = Pd(II) and Pd(IV) complexes derived from 2,6-diacetylpyridine: catalytic applications / Francisco Juliá Hernández; directores, José Vicente Soler, Aurelia Arcas García.

Texto en inglés, resumen en español.Tesis-Universidad de Murcia.Consulte la tesis en: BCA. GENERAL. ARCHIVO UNIVERSITARIO. TM 4372

Attaching CF3 groups to organic molecules using trifluoroacetates via ion-shielding photoelectrocatalysis

© 2024 Science China Press and Springer. This document is the Accepted version of a Published Work that appeared in final form in Science China Chemistry. To access the final edited and published work see https://doi.org/10.1007/s11426-024-2177-