Resultados de investigación

The divergent reactivity of the cationic iridium complex [(η5-C5Me5)IrCl(PMe2ArDipp2)]+ (ArDipp2 = C6H3–2,6-(C6H3–2,6-iPr2)2) toward organolithium and Grignard reagents is described. The noninnocent behavior of the Cp* ligand, a robust spectator in the majority of stoichiometric and catalytic reactions, was manifested by its unforeseen electrophilic character toward organolithium reagents LiMe, LiEt, and LinBu. In these unconventional transformations, the metal center is only indirectly involved by means of the Ir(III)/Ir(I) redox cycle. In the presence of less nucleophilic organolithium reagents, the Cp* ligand also exhibits noninnocent behavior undergoing facile deprotonation, which is also concomitant with the reduction of the metal center. In turn, the weaker alkylating agents EtMgBr and MeMgBr effectively achieve the alkylation of the metal center. These reactive iridium(III) alkyls partake in subsequent reactions: while the ethyl complex undergoes β-H elimination, the methyl derivative releases methane by a remote C–H bond activation. Computational studies, including the quantum theory of atoms in molecules (QTAIM), support that the preferential activation of the non-benzylic C–H bonds takes place via sigma-bond metathesis., Peer reviewed

3 pages. -- This PDF file includes: Figure S1. Figure S1. Effect of tunicamycin on Orai1 plasma membrane expression; Table 1. Table S1. Tunicamycin attenuates Orai1 and STIM1 protein expression in MCF10A and MDA-MB-231 cells., Peer reviewed

9 pages. -- Encoding visualization. -- Figure S1-S14. -- Table S1. Cell type, number of samples detail, and percentage of samples above or below the encoding-based threshold of Melanoma dataset during the testing phase., Peer reviewed

Under a Creative Commons license BY 4.0 deed., Table S1. Raman shift (cm-1) of the G, D, D’ and D’’ from Raman spectra deconvolution and ID/IG intensity ratio. Table S2. Surface carbon, oxygen, nitrogen, cobalt and titanium contents and C/N, Co/N and Ti/N ratios calculated by XPS of the electrocatalysts and the relative content (%) of the deconvoluted peaks for N1s, Co2p and Ti2p. Figure S1. High-resolution C1s core level of NGC, Ti/NGC, Co/NGC and TiCo/NGC composites. Figure S2. LSV at 0.005 V s−1 in an O2-saturated 0.1 M NaOH solution, recorded using different electrode rotating rates indicated in the legend (rpm). (A) NGC, (B) Ti/NGC, (C) Co/NGC, (D) TiCo/NGC. Figure S3. Koutecky−Levich diagrams obtained between 0.3 and 0.56 V vs RHE for each composite. (A) NGC, (B) Ti/NGC, (C) Co/NGC, (D) TiCo/NGC. Figure S4. Koutecky−Levich diagrams obtained between 0.6 and 0.78 V vs RHE for each composite. (A) NGC, (B) Ti/NGC, (C) Co/NGC, (D) TiCo/NGC., The authors wish to acknowledge the grants PID2020-115848RB-C21 and PID2020-115848RB-C22 funded by MCIN/AEI/10.13039/501100011033, and the Spanish National Research Council (CSIC) through the i-LINK + Programme (i-LINK1106)., Peer reviewed

1. NMR Spectra.-- 2. Kinetic Isotopic Effect (KIE) Experiments.-- 3. X-Ray Characterization.-- 4. Computational Studies.-- 5. References., Peer reviewed

1. Experimental procedures.-- 2. NMR spectra.-- 3. Crystal structure determinations.-- 4. Mass spectrometry.-- 5. Variable temperatura van´t Hoff study of the equilibrium of 9 and 2c with 10c.-- 6. Computational details.-- 7. Referencias., Peer reviewed

1. NMR spectroscopic experiments.-- 2. Catalytic experiments.-- 3. Crystal structure determinations.-- 4. References., Peer reviewed

1. General considerations.-- 2. Synthesis and characterization of new compounds.-- 3. NMR spectra of new compounds.-- 4. Crystal structure determinations.-- 5. TON and TOF determination.-- 6. Computational studies.-- 7. References., Peer reviewed

Peer reviewed

Table S1. Structural features of donor-acceptor CO2 adducts from metal-free acid/base pairs.-- Table S2. Structural features of donor-acceptor CO2 adducts from transition metal-main group pairs.-- Table S3. Structural features of donor-acceptor CO2 adducts from transition metal-main group pairs., Peer reviewed