An N-Heterocyclic Quinodimethane: A Strong Organic Lewis Base Exhibiting Diradical Reactivity.

We report the preparation of a new organic σ-donor with a C6H4-linker between an N-heterocyclic carbene (NHC) and an exocyclic methylidene group, which we term N-heterocyclic quinodimethane (NHQ). The aromatization of the C6H4-linker provides a decisive driving force for the reaction of the NHQ with an electrophile and renders the NHQ significantly more basic than analogous NHCs or N-heterocyclic olefins (NHOs), as shown by DFT computations and competition experiments. In solution, the NHQ undergoes an unprecedented dehydrogenative head-to-head dimerization by C-C coupling of the methylidene groups. DFT computations indicate that this reaction proceeds via an open-shell singlet pathway revealing the diradical character of the NHQ. The product of this dimerization can be described as conjugated N-heterocyclic bis-quinodimethane, which according to cyclic voltammetry is a strong organic reducing agent (E1/2=-1.71 V vs. Fc/Fc+) and exhibits a remarkable small singlet-triplet gap of ΔES→T=4.4 kcal mol-1.

Synthesis and characterization of a formal 21-electron cobaltocene derivative.

Metallocenes are highly versatile organometallic compounds. The versatility of the metallocenes stems from their ability to stabilize a wide range of formal electron counts. To date, d-block metallocenes with an electron count of up to 20 have been synthesized and utilized in catalysis, sensing, and other fields. However, d-block metallocenes with more than formal 20-electron counts have remained elusive. The synthesis and isolation of such complexes are challenging because the metal-carbon bonds in d-block metallocenes become weaker with increasing deviation from the stable 18-electron configuration. Here, we report the synthesis, isolation, and characterization of a 21-electron cobaltocene derivative. This discovery is based on the ligand design that allows the coordination of an electron pair donor to a 19-electron cobaltocene derivative while maintaining the cobalt-carbon bonds, a previously unexplored synthetic approach. Furthermore, we elucidate the origin of the stability, redox chemistry, and spin state of the 21-electron complex. This study reveals a synthetic method, structure, chemical bonding, and properties of the 21-electron metallocene derivative that expands our conceptual understanding of d-block metallocene chemistry. We expect that this report will open up previously unexplored synthetic possibilities in d-block transition metal chemistry, including the fields of catalysis and materials chemistry.

The entropic penalty for associative reactions and their physical treatment during routine computations.

A systematic study of the entropic penalty for associative reactions is presented. It is shown that computed solution-phase Gibbs free energies typically overestimate entropic contributions. This entropic penalty for associative reactions in solution, i.e., if the number of particles decreases along the reaction coordinate (sum of stoichiometric numbers ), originates from the insufficient treatment of entropic effects by implicit solvent models. We propose an additive correction scheme to Gibbs free energies that is suitable for routine applications by non-expert users. This correction is based on Garza's formalism for the solution-phase entropy [A. J. Garza, J. Chem. Theory Comput., 2019, 15, 3204.] that is physically sound and embedded into an efficient black-box type algorithm. To critically evaluate the entropic penalty and its proposed treatment, we compiled an experimental benchmark set of 31 ΔrG and 22 in 15 different solvents. Using a representative best-practice computational protocol (at wave function theory (WFT) based DLPNO-CCSD(T) and density functional theory (DFT) based revDSD-PBEP86-D4 level with an implicit solvent model), we determined a sizeable entropic penalty ranging from 2-11 kcal mol-1. Using the correction scheme presented herein, the entropic penalty is corrected to the chemical accuracy of ≤1 kcal mol-1 (WFT and DFT). The same applies to at the WFT level. Barriers at the DFT level are overestimated by 2 kcal mol-1 (classic) and underestimated by 2 kcal mol-1 (corrected). This effect is attributed to the finding that barriers computed at the DFT level are systematically 2-3 kcal mol-1 lower than barriers obtained with WFT.

"Through-Space" Relativistic Effects on NMR Chemical Shifts of Pyridinium Halide Ionic Liquids.

We have investigated, using two-component relativistic density functional theory (DFT) at ZORA-SO-BP86 and ZORA-SO-PBE0 level, the occurrence of relativistic effects on the 1 H, 13 C, and 15 N NMR chemical shifts of 1-methylpyridinium halides [MP][X] and 1-butyl-3-methylpyridinium trihalides [BMP][X3 ] ionic liquids (ILs) (X=Cl, Br, I) as a result of a non-covalent interaction with the heavy anions. Our results indicate a sizeable deshielding effect in ion pairs when the anion is I- and I3- . A smaller, though nonzero, effect is observed also with bromine while chlorine based anions do not produce an appreciable relativistic shift. The chemical shift of the carbon atoms of the aromatic ring shows an inverse halogen dependence that has been rationalized based on the little C-2s orbital contribution to the σ-type interaction between the cation and anion. This is the first detailed account and systematic theoretical investigation of a relativistic heavy atom effect on the NMR chemical shifts of light atoms in the absence of covalent bonds. Our work paves the way and suggests the direction for an experimental investigation of such elusive signatures of ion pairing in ILs.