Sigma-Noninnocence:Masked Phenyl-Cation Transfer at Formal Ni-IV

Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of -2 at a transition-metal center. For a series of formal high-valent Ni-IV complexes, aryl-CF3 bond-forming reductive elimination was reported to occur readily (Bour et al. J. Am. Chem. Soc. 2015, 137, 8034-8037). We report a computational analysis of this reaction and find that, unexpectedly, the formal Ni-IV centers are better described as approaching a +II oxidation state, originating from highly covalent metal-ligand bonds, a phenomenon attributable to sigma-noninnocence. A direct consequence is that the elimination of aryl-CF3 products occurs in an essentially redox-neutral fashion, as opposed to a reductive elimination. This is supported by an electron flow analysis which shows that an anionic CF3 group is transferred to an electrophilic aryl group. The uncovered role of sigma-noninnocence in metal-ligand bonding, and of an essentially redox-neutral elimination as an elementary organometallic reaction step, may constitute concepts of broad relevance to organometallic chemistry

Blatter Radicals as Bipolar Materials for Symmetrical Redox-Flow Batteries

[Image: see text] Redox-active organic molecules are promising charge-storage materials for redox-flow batteries (RFBs), but material crossover between the posolyte and negolyte and chemical degradation are limiting factors in the performance of all-organic RFBs. We demonstrate that the bipolar electrochemistry of 1,2,4-benzotriazin-4-yl (Blatter) radicals allows the construction of batteries with symmetrical electrolyte composition. Cyclic voltammetry shows that these radicals also retain reversible bipolar electrochemistry in the presence of water. The redox potentials of derivatives with a C(3)-CF(3) substituent are the least affected by water, and moreover, these compounds show >90% capacity retention after charge/discharge cycling in a static H-cell for 7 days (ca. 100 cycles). Testing these materials in a flow regime at a 0.1 M concentration of the active material confirmed the high cycling stability under conditions relevant for RFB operation and demonstrated that polarity inversion in a symmetrical flow battery may be used to rebalance the cell. Chemical synthesis provides insight in the nature of the charged species by spectroscopy and (for the oxidized state) X-ray crystallography. The stability of these compounds in all three states of charge highlights their potential for application in symmetrical organic redox-flow batteries

Bipolar Verdazyl Radicals for Symmetrical Batteries: Properties and Stability in All States of Charge

Redox flow batteries based on organic electrolytes are promising energy storage devices, but stable long-term cycling is often difficult to achieve. Bipolar organic charge-storage materials allow the construction of symmetrical flow batteries (i. e., with identical electrolyte composition on both sides), which is a strategy to mitigate crossover-induced degradation. One such class of bipolar compounds are verdazyl radicals, but little is known on their stability/reactivity either as the neutral radical, or in the charged states. Here, we study the chemical properties of a Kuhn-type verdazyl radical ( 1 ) and the oxidized/reduced form ( 1 +/−). Chemical synthesis of the three redox-states provides spectroscopic characterization data, which are used as reference for evaluating the composition of the electrolyte solutions of an H-cell battery during/after cycling. Our data suggest that, rather than the charged states, the decomposition of the parent verdazyl radical is responsible for capacity fade. Kinetic experiments and DFT calculations provide insight in the decomposition mechanism, which is shown to occur by bimolecular disproportionation to form two closed-shell products (leuco-verdazyl 1H and triazole derivative 2 )

CCDC 2098287: Experimental Crystal Structure Determination

Related Article: Jelte S. Steen, Jules L. Nuismer, Vytautas Eiva, Albert E. T. Wiglema, Nicolas Daub, Johan Hjelm, Edwin Otten|2022|J.Am.Chem.Soc.|||doi:10.1021/jacs.1c1354

CCDC 2098289: Experimental Crystal Structure Determination

Related Article: Jelte S. Steen, Jules L. Nuismer, Vytautas Eiva, Albert E. T. Wiglema, Nicolas Daub, Johan Hjelm, Edwin Otten|2022|J.Am.Chem.Soc.|||doi:10.1021/jacs.1c1354

CCDC 2098288: Experimental Crystal Structure Determination

Related Article: Jelte S. Steen, Jules L. Nuismer, Vytautas Eiva, Albert E. T. Wiglema, Nicolas Daub, Johan Hjelm, Edwin Otten|2022|J.Am.Chem.Soc.|||doi:10.1021/jacs.1c1354

Proceedings of the 4th World Conference on Research Integrity

CITATION: O’Brien, S. P., et al. 2016. Proceedings of the 4th World Conference on Research Integrity. Research Integrity and Peer Review, 1:9, doi:10.1186/s41073-016-0012-9.The original publication is available at https://researchintegrityjournal.biomedcentral.comThese Proceedings contain the abstracts of the presentations given at the 4th World Conference in concurrent sessions, partner symposia, and poster sessions. Also included are summaries of the discussions in three focus tracks, which allowed delegates to consider and work on questions about the roles of funders, institutions, and countries in improving research systems and strengthening research integrity. Videos of the plenary presentations are available at the conference website (www.wcri2015.org).https://researchintegrityjournal.biomedcentral.com/articles/10.1186/s41073-016-0012-