Taming the Antiferromagnetic Beast: Computational Design of Ultrashort Mn-Mn Bonds Stabilized by N-Heterocyclic Carbenes.
Ontology highlight
ABSTRACT:
SUBMITTER: Francisco MAS
PROVIDER: S-EPMC8456913 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:Aluminum chalcogenides are mostly encountered in the form of bulk aluminum oxides that are structurally diverse but typically consist of networks with high lattice energy in which the chalcogen atoms bridge the metal centres. This makes their molecular congeners difficult to synthesize because of a pronounced tendency for oligomerization. Here we describe the isolation of the monotopic aluminum chalcogenide (L(Dip)N)AlTe(L(Et))2 (L(Dip)=1,3-(2,6-diisopropylphenyl)-imidazolin-2-imine, L(Et)=1,3-diethyl-4,5-dimethyl-imidazolin-2-ylidene). Unique features of (L(Dip)N)AlTe(L(Et))2 are the terminal position of the tellurium atom, the shortest aluminum-tellurium distance hitherto reported for a molecular complex and the highest bond order reported for an interaction between these elements, to the best of our knowledge. At elevated temperature (L(Dip)N)AlTe(L(Et))2 equilibrates with dimeric {(L(Dip)N)AlTe(L(Et))}2 in which the chalcogen atoms assume their common role as bridges between the metal centres. These findings demonstrate that (L(Dip)N)AlTe(L(Et))2 comprises the elusive Al=Te double bond in the form of an N-heterocyclic carbene-stabilized species.
| S-EPMC4674676 | biostudies-literature
Project description:Cationic d0 group 6 olefin metathesis catalysts have been recently shown to display in most instances superior activity in comparison to their neutral congeners. Furthermore, their catalytic performance is greatly improved upon immobilization on silica. In this context, we have developed the new family of molecular cationic molybdenum oxo alkylidene complexes stabilized by N-heterocyclic carbenes of the general formula [Mo(O)(CHCMe3)(IMes)(OR)[X-]] (IMes = 1,3-dimesitylimidazol-2-ylidene; R = 1,3-dimesityl-C6H3, C6F5; X- = B(3,5-(CF3)2C6H3)4 -, B(ArF)4, tetrakis(perfluoro-t-butoxy)aluminate (PFTA)). Immobilization of [Mo(O)(CHCMe3)(IMes)(O-1,3-dimesityl-C6H3)+B(ArF)4 -] on silica via surface organometallic chemistry yields an active alkene metathesis catalyst that shows the highest productivity towards terminal olefins amongst all existing molybdenum oxo alkylidene catalysts.
| S-EPMC9337747 | biostudies-literature
Project description:Treatment with CD19 or CD22-targeted chimeric antigen receptor-engineered T (CD19/CD22 CAR-T) cells achieve complete responses in 60-90% of adults and children with refractory or relapsed (R/R) acute lymphoblastic leukemia (ALL). This led to the approval of tisagenlecleucel (Kymriah) by the FDA and several European regulatory agencies in ALL patients up to 25 years of age. Although CAR T-cell therapy is likely to transform the ALL therapeutic landscape, its development and wide dissemination have been impacted by the occurrence of significant toxicities; namely, cytokine release syndrome (CRS) and Immune effector cell-Associated Neurotoxicity Syndrome (ICANS) have been reported at higher rates in ALL patients compared to other B cell malignancies, particularly in the adult population. Here, we review recent data suggesting a significant proportion of ALL patients are at risk of developing severe, sometimes life-threatening, CRS, and ICANS after CD19 and CD22 CAR T-cell therapy. After describing the key clinical and laboratory features of severe CRS and ICANS, we explore the disease and treatment-related factors that may predict the severity of these toxicities. Last, we review strategies under investigation in the prophylactic and therapeutic settings to improve the safety of CAR T-cells for ALL.
| S-EPMC8592274 | biostudies-literature
Project description:The electron-deficient pentaarylborole 1-(2',4',6'-tris(trifluoromethyl)phenyl)-2,3,4,5-tetraphenylborole (1) has been synthesised with the long-term aim of developing borole-based optoelectronic materials. The bulky 2,4,6-tris(trifluoromethyl)phenyl (FMes) group on the boron atom of 1 significantly improves (>600 times) its air stability relative to its mesityl analogue. Moreover, 1 shows good thermal stability without undergoing the dimerisation or isomerisation reactions reported for some other boroles. A triarylborole analogue (2), belonging to a new class of borole with the 3- and 4-positions of the BC4 ring linked by a -(CH2)3- group, has also been synthesised to elucidate the influence of carbon-bonded substituents on the stability of boroles. Both boroles were prepared through the reaction of Li[FMesBF3] and divinyldilithium reagents, a new and general method for borole syntheses. Compound 2 was found to isomerise through a [1,3]-H shift and double-bond rearrangement to an s-trans-butadienylborane species under highly basic (NaOH) conditions. The increased steric crowding at the boron centre through incorporation of the FMes group does not preclude binding of Lewis bases to either 1 or 2, as demonstrated by their fully reversible binding of pyridine. Interestingly, 1 exhibits a blue-shifted absorption spectrum, as compared with its mesityl analogue, a result contrary to previous understanding of the influence of substituent electronics on the absorption spectra of boroles. Most importantly, these boroles exhibit much greater air-stability than previously reported analogues without sacrificing the strong electron-accepting ability that makes boroles so attractive; indeed, 1 and 2 have very low reduction potentials of -1.52 and -1.69 eV vs. Fc/Fc+, respectively.
| S-EPMC5523080 | biostudies-other
Project description:In this work the mechanism of the aldehyde umpolung reactions, catalyzed by azolium cations in the presence of bases, was studied through computational methods. Next to the mechanism established by Breslow in the 1950s that takes effect through the formation of a free carbene, we have suggested that these processes can follow a concerted asynchronous path, in which the azolium cation directly reacts with the substrate, avoiding the formation of the carbene intermediate. We hereby show that substituting the azolium cation, and varying the base or the substrate do not affect the preference for the concerted reaction mechanism. The concerted path was found to exhibit low barriers also for the reactions of thiamine with model substrates, showing that this path might have biological relevance. The dominance of the concerted mechanism can be explained through the specific structure of the key transition state, avoiding the liberation of the highly reactive, and thus unstable carbene lone pair, whereas activating the substrate through hydrogen-bonding interactions. Polar and hydrogen-bonding solvents, as well as the presence of the counterions of the azolium salts facilitate the reaction through carbenes, bringing the barriers of the two reaction mechanisms closer, in many cases making the concerted path less favorable. Thus, our data show that by choosing the exact components in a reaction, the mechanism can be switched to occur with or without carbenes.
| S-EPMC7496998 | biostudies-literature
Project description:IPr (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) represents the most important NHC (NHC = N-heterocyclic carbene) ligand throughout the field of homogeneous catalysis. Herein, we report the synthesis, catalytic activity, and full structural and electronic characterization of novel, sterically-bulky, easily-accessible NHC ligands based on the hash peralkylation concept, including IPr#, Np# and BIAN-IPr#. The new ligands have been commercialized in collaboration with Millipore Sigma: IPr#HCl, 915653; Np#HCl; 915912; BIAN-IPr#HCl, 916420, enabling broad access of the academic and industrial researchers to new ligands for reaction optimization and screening. In particular, the synthesis of IPr# hinges upon cost-effective, modular alkylation of aniline, an industrial chemical that is available in bulk. The generality of this approach in ligand design is demonstrated through facile synthesis of BIAN-IPr# and Np#, two ligands that differ in steric properties and N-wingtip arrangement. The broad activity in various cross-coupling reactions in an array of N-C, O-C, C-Cl, C-Br, C-S and C-H bond cross-couplings is demonstrated. The evaluation of steric, electron-donating and π-accepting properties as well as coordination chemistry to Au(i), Rh(i) and Pd(ii) is presented. Given the tremendous importance of NHC ligands in homogenous catalysis, we expect that this new class of NHCs will find rapid and widespread application.
| S-EPMC8356752 | biostudies-literature
Project description:Collagen is a force-bearing, hierarchical structural protein important to all connective tissue. In tendon collagen, high load even below macroscopic failure level creates mechanoradicals by homolytic bond scission, similar to polymers. The location and type of initial rupture sites critically decide on both the mechanical and chemical impact of these micro-ruptures on the tissue, but are yet to be explored. We here use scale-bridging simulations supported by gel electrophoresis and mass spectrometry to determine breakage points in collagen. We find collagen crosslinks, as opposed to the backbone, to harbor the weakest bonds, with one particular bond in trivalent crosslinks as the most dominant rupture site. We identify this bond as sacrificial, rupturing prior to other bonds while maintaining the material's integrity. Also, collagen's weak bonds funnel ruptures such that the potentially harmful mechanoradicals are readily stabilized. Our results suggest this unique failure mode of collagen to be tailored towards combatting an early onset of macroscopic failure and material ageing.
| S-EPMC10097693 | biostudies-literature
Project description:In the presence of a chiral azolium salt (10 mol %), enols and ynals undergo a highly enantioselective annulation reaction to form enantiomerically enriched dihydropyranones via an N-heterocyclic carbene catalyzed variant of the Claisen rearrangement. Unlike other azolium-catalyzed reactions, this process requires no added base to generate the putative NHC-catalyst, and our investigations demonstrate that the counterion of the azolium salt plays a key role in the formation of the catalytically active species. Detailed kinetic studies eliminate a potential 1,4-addition as the mechanistic pathway; the observed rate law and activation parameters are consistent with a Claisen rearrangement as the rate-limiting step. This catalytic system was applied to the synthesis of enantioenriched kojic acid derivatives, a reaction of demonstrated synthetic utility for which other methods for catalytic enantioselective Claisen rearrangements have not provided a satisfactory solution.
| S-EPMC2902991 | biostudies-literature
Project description:Although the self-assembly of organic ligands on gold has been dominated by sulfur-based ligands for decades, a new ligand class, N-heterocyclic carbenes (NHCs), has appeared as an interesting alternative. However, fundamental questions surrounding self-assembly of this new ligand remain unanswered. Herein, we describe the effect of NHC structure, surface coverage, and substrate temperature on mobility, thermal stability, NHC surface geometry, and self-assembly. Analysis of NHC adsorption and self-assembly by scanning tunneling microscopy and density functional theory have revealed the importance of NHC-surface interactions and attractive NHC-NHC interactions on NHC monolayer structures. A remarkable way these interactions manifest is the need for a threshold NHC surface coverage to produce upright, adatom-mediated adsorption motifs with low surface diffusion. NHC wingtip structure is also critical, with primary substituents leading to the formation of flat-lying NHC2Au complexes, which have high mobility when isolated, but self-assemble into stable ordered lattices at higher surface concentrations. These and other studies of NHC surface chemistry will be crucial for the success of these next-generation monolayers.
| S-EPMC8241988 | biostudies-literature
Project description:Atomically precise tailoring of interface structures is crucial for developing functional materials. We demonstrate an N-heterocyclic carbene (NHC) based molecular tool, which modifies the structure of a gold surface with atomic accuracy by the formation of gold nanorods. After adsorption on the gold surface, individual surface atoms are pulled out by the NHCs, generating single-atom surface defects and mobile NHC-Au species. Atomistic calculations reveal that these molecular "ballbots" can act as assembling tools to dislocate individual surface atoms. The predicted functionality of these carbene-based complexes is confirmed by scanning tunneling microscopy measurements. Cooperative operation of these NHC-Au species induces a step-wise formation of gold nanorods. Consequently, the surface is re-structured by a zipper-type mechanism. Our work presents a foundation to utilize molecular-based nanotools to design surface structures.
| S-EPMC7702088 | biostudies-literature