Dianionic and Neutral Diboron-Centered Classical Diradicaloids.

Herein, we report the syntheses and electronic structures of crystalline dianionic as well as neutral diboron-centered classical diradicaloids as boron analogues of classical Thiele, Chichibabin, and Müller (this only for dianionic diradicaloids!) hydrocarbons. These are based on borane radical anion and NHC-stabilized boryl radical spin carriers, respectively. All these dianionic diboron-centered diradicaloids exhibit triplet population at room temperature regardless of the π-conjugated spacer: p-phenylene, p,p'-biphenylene, or p,p″-terphenylene. In the case of neutral diboron-centered diradicaloids, the employed π-conjugated spacer plays a crucial role for the triplet population at room temperature: EPR inactive for p-phenylene vs EPR active for p,p'-biphenylene. The findings emphasize the importance of the spin carriers for the resulting ground-state: borane radical anion vs NHC-stabilized boryl radical along with the pivotal role of the π-conjugated spacer as spin-coupler between two spins. Notably, 100 years (a century) after the first report by Krause of the triphenyl borane radical-anion, being isoelectronic to the triphenylmethyl radical, we convey borane radical anion-based diradicaloids. Furthermore, while donor-stabilized boryl radicals were introduced in the 1980s by Giles and Roberts, said concept is herewith being extended to NHC-stabilized boryl radical-based diradicaloids.

Dynamics and Coordination of a P2N2 Ligand - from Twisted Conformation to Chelation.

Based on their general spacial flexibility, their Lewis and Brønsted basicity, and ability to mimic second sphere effects the 1,5-diaza-3,7-diphosphacyclooctane ligand family and their complexes have regained substantial scientific interest. It was now possible to structurally analyze a recently reported member of this family with p-tolyl and t-butyl substituents on P and N, respectively, (P2 p-tolN2 tBu). Notably, the ligand crystallizes with a 'twisted' backbone. This compound is the very first of its kind to have been unambiguously characterized with regard to its chemical and molecular structure as being in this conformation. A temperature-dependent NMR study provides insight into the molecular dynamics of two isomers in solution, which are most likely also both twisted, as judged by the observed limited reactivity. Despite the in principle unfavorable conformation of the free ligand, it was successfully chelated to tungsten and molybdenum centers in mononuclear carbonyl complexes. The ligand, a derivative thereof and four new complexes were comprehensively characterized and analyzed in comparison. This includes single crystal XRD molecular structures of P2 p-tolN2 tBu and all four complexes. P2 p-tolN2 tBu, regardless of its twisted conformation, is able to coordinate to metal centers given that enough energy (heat) for a conformational change is provided.

Comment on "Disclosing Cyclic(Alkyl)(Amino)Carbenes as a One-Electron Reductant: Synthesis of Acyclic(Amino)(Aryl)Carbene-Based Kekulé Diradicaloids".

This correspondence addresses a misassignment of an EPR spectrum of 2 in a recent publication (Chem. Eur. J. 2022, 28, e202104567) by Dr. Jana and co-workers. The original authors have prepared this correspondence together with Dr. Korth.

Carbodicarbenes and Striking Redox Transitions of their Conjugate Acids: Influence of NHC versus CAAC as Donor Substituents.

Herein, a new type of carbodicarbene (CDC) comprising two different classes of carbenes is reported; NHC and CAAC as donor substituents and compare the molecular structure and coordination to Au(I)Cl to those of NHC-only and CAAC-only analogues. The conjugate acids of these three CDCs exhibit notable redox properties. Their reactions with [NO][SbF6 ] were investigated. The reduction of the conjugate acid of CAAC-only based CDC with KC8 results in the formation of hydrogen abstracted/eliminated products, which proceed through a neutral radical intermediate, detected by EPR spectroscopy. In contrast, the reduction of conjugate acids of NHC-only and NHC/CAAC based CDCs led to intermolecular reductive (reversible) carbon-carbon sigma bond formation. The resulting relatively elongated carbon-carbon sigma bonds were found to be readily oxidized. They were, thus, demonstrated to be potent reducing agents, underlining their potential utility as organic electron donors and n-dopants in organic semiconductor molecules.

Synthesis of Seven Indolizine-Derived Pentathiepines: Strong Electronic Structure Response to Nitro Substitution in Position C-9.

Seven new 1,2,3,4,5-pentathiepino[6,7-a]indolizines were synthesized in which the pentathiepine moieties bear an indolizine backbone that is derivatized from C-H to F-, Cl-, Br-, I-, NO2-, and CH3-substitutions, respectively, in a meta position relative to the aza group on the pyridine moiety. Their preparation took place via two common steps: (i) a Sonogashira coupling between (4-substituted) 2-bromo- or 2-chloropyridines and propynyl 3,3-diethylacetal, and (ii) a ring closing reaction mediated by a molybdenum oxo-bistetrasulfido complex and elemental sulfur. The latter simultaneously facilitates the 1,2,3,4,5-pentathiepino chain/ring- and indolizine ring-formations. The fluoro derivative was addressed with 2-bromo-5-aminopyridine as the starting material via a Sandmeyer reaction. The iodo derivative was obtained from 5-bromo-2-alkynylpiridine using a metal-assisted variation of the Finkelstein reaction. The requirement to explore different reaction conditions and the varied respective yields of the final products are discussed. The influence of the distinct substitutions on the pyridine moieties, their electronic structures, and respective chemical properties was investigated through a set of spectroscopic/analytical characterizations. Intriguingly, in all cases, the nitro-substituted derivative exhibited a distinct behavior compared to the six other investigated derivatives, which was also addressed computationally. All seven new pentathiepines were crystallized, and their respective molecular structures were determined using single crystal X-ray diffraction. These structures are compared and discussed as are their respective packing patterns.

Fine-Tuning Redox Properties of Heteroleptic Molybdenum Complexes through Ligand-Ligand-Cooperativity.

Heteroleptic molybdenum complexes bearing 1,5-diaza-3,7-diphosphacyclooctane (P2 N2 ) and non-innocent dithiolene ligands were synthesized and electrochemically characterized. The reduction potentials of the complexes were found to be fine-tuned by a synergistic effect identified by DFT calculations as ligand-ligand cooperativity via non-covalent interactions. This finding is supported by electrochemical studies combined with UV/Vis spectroscopy and temperature-dependent NMR spectroscopy. The observed behavior is reminiscent of enzymatic redox modulation using second ligand sphere effects.

Bis-Olefin Based Crystalline Schlenk Hydrocarbon Diradicals with a Triplet Ground State.

A modular approach for the synthesis of isolable crystalline Schlenk hydrocarbon diradicals from m-phenylene bridged electron-rich bis-triazaalkenes as synthons is reported. EPR spectroscopy confirms their diradical nature and triplet electronic structure by revealing a half-field signal. A computational analysis confirms the triplet state to be the ground state. As a proof-of-principle for the modular methodology, the 4,6-dimethyl-m-phenylene was further utilized as a coupling unit between two alkene motifs. The steric conjunction of the 4,6-dimethyl groups substantially twists the substituents at the nonbonding electron bearing centers relative to the central coupling m-phenylene motif. As a result, the spin delocalization is decreased and the exchange coupling between the two unpaired spins, hence, significantly reduced. Notably, 108 years after Schlenk's m-phenylene-bis(diphenylmethyl) synthesis as a diradical, for the first time we were able to isolate its derivative with the same spacer, i.e. m-phenylene, between two radical centers in a crystalline form.

Disclosing Cyclic(Alkyl)(Amino)Carbenes as One-Electron Reductants: Synthesis of Acyclic(Amino)(Aryl)Carbene-Based Kekulé Diradicaloids.

Herein, we disclose cyclic(alkyl)(amino)carbenes (CAACs) to be one-electron reductants under the formation of a transient radical cation as indicated by EPR spectroscopy. The disclosed CAAC reducing reactivity was used to synthesize acyclic(amino)(aryl)carbene-based Thiele and Chichibabin hydrocarbons, a new class of Kekulé diradicaloids. The results demonstrate CAACs to be potent organic reductants. Notably, the acyclic(amino)(aryl)carbene-based Chichibabin's hydrocarbon shows an appreciable population of the triplet state at room temperature, as evidenced by both variable-temperature NMR and EPR spectroscopy.

Inspired by Nature-Functional Analogues of Molybdenum and Tungsten-Dependent Oxidoreductases.

Throughout the previous ten years many scientists took inspiration from natural molybdenum and tungsten-dependent oxidoreductases to build functional active site analogues. These studies not only led to an ever more detailed mechanistic understanding of the biological template, but also paved the way to atypical selectivity and activity, such as catalytic hydrogen evolution. This review is aimed at representing the last decade's progress in the research of and with molybdenum and tungsten functional model compounds. The portrayed systems, organized according to their ability to facilitate typical and artificial enzyme reactions, comprise complexes with non-innocent dithiolene ligands, resembling molybdopterin, as well as entirely non-natural nitrogen, oxygen, and/or sulfur bearing chelating donor ligands. All model compounds receive individual attention, highlighting the specific novelty that each provides for our understanding of the enzymatic mechanisms, such as oxygen atom transfer and proton-coupled electron transfer, or that each presents for exploiting new and useful catalytic capability. Overall, a shift in the application of these model compounds towards uncommon reactions is noted, the latter are comprehensively discussed.

Realizing 1,1-Dehydration of Secondary Alcohols to Carbenes: Pyrrolidin-2-ols as a Source of Cyclic (Alkyl)(Amino)Carbenes.

Herein we report secondary pyrrolidin-2-ols as a source of cyclic (alkyl)(amino)carbenes (CAAC) for the synthesis of CAAC-CuI -complexes and cyclic thiones when reacted with CuI -salts and elemental sulfur, respectively, under reductive elimination of water from the carbon(IV)-center. This result demonstrates a convenient and facile access to CAAC-based CuI -salts, which are well known catalysts for different organic transformations. It further establishes secondary alcohols to be a viable source of carbenes-realizing after 185 years Dumas' dream who tried to prepare the parent carbene (CH2 ) by 1,1-dehydration of methanol. Addressed is also the reactivity of water towards CAACs, which proceeds through an oxidative addition of the O-H bond to the carbon(II)-center. This emphasizes the ability of carbon-compounds to mimic the reactivity of transition-metal complexes: reversible oxidative addition and reductive elimination of the O-H bond to/from the C(II)/C(IV)-centre.

Bis-[cyclic(alkyl)(amino)carbene]-derived diradicals.

Crystalline polymeric structures of trans-1,4-cyclohexylene bridged N-tethered bis-CAACs in the form of their LiOTf adducts were synthesized and isolated. These were further used as building blocks for the synthesis of crystalline (amino)(carboxy)-based diradicals. The triplet diradical character of these compounds was unambiguously confirmed by the presence of a half-field signal in their EPR spectra. Theoretical calculations show that the singlet state is marginally more stable than the triplet state.

Reduction of 2-H-substituted pyrrolinium cations: the carbon-carbon single bond in air stable 2,2'-bipyrrolidines as a two-electron-source.

Reduction of 2-H-substituted pyrrolinium cations via initially formed secondary radicals results in either dimerisation or H-abstracted products, while the outcome depends on the N-substituents. The resultant central carbon-carbon single bond in the dimerised 2,2'-bipyrrolidine derivatives can be oxidised chemically and electrochemically. The notably air and moisture-stable dimers were subsequently utilised as a source of two electrons in various chemical transformations.

Introducing an orthogonally polarized electron-rich alkene: synthesis of a zwitterionic boron-containing π-conjugated system.

The synthesis of an alkene is reported which is concurrently twisted (twist angle = 86.6(8)°), push-pull (dipole moment = 7.48 D), and electron-rich (E1/2 = -1.45 V and -0.52 V vs. Fc/Fc+) in nature, comprising a unique trinity combination for the alkene class of compounds. Subsequently, this newly synthesized alkene-motif was used as a donor for the synthesis of a zwitterionic boron-containing π-conjugated compound (dipole moment = 12.17 D) through an intramolecular charge transfer process exploiting the π-conjugated donor-acceptor system.

Air and Moisture Stable para- and ortho-Quinodimethane Derivatives Derived from bis-N-Heterocyclic Olefins.

Herein we report the development of a new methodology for the synthesis of various quinodimethane derivatives under two-electron oxidation of bis-N-heterocyclic olefins linked by different π-conjugated aromatic spacers. In case of para- and ortho-phenylene bridge, we obtained air and moisture stable diimidazolium para- and ortho-quinodimethane derivatives. Analogues of the para-phenylene spacer such as tetrafluoro-p-phenylene and p-anthracene also led to the corresponding air and moisture stable quinodimethane derivatives. This emphasizes the influence of imidazolium substituents which facilitate the air and moisture stability of the quinodimethane derivatives. Differences were observed for the electron transfer processes: two one-electron vs one two-electron redox transitions between bis-N-heterocyclic olefins and diimidazolium-quinodimethanes depending on the employed π-conjugated aromatic spacer. The formation of the π-conjugated radical-cations, transient redox intermediates between bis-N-heterocyclic olefins and diimidazolium-quinodimethanes, was addressed by an EPR investigation.

An Air-Stable Alkene-Derived Organic Radical Cation.

Alkenes are known to undergo oxidation to radical cations and dications. The radical cations are often highly reactive and not stable under air. Herein, we report the synthesis, isolation, characterization, and molecular structure of an alkene-derived radical cation A, which is stable in air both in the solid state and in solution. The access to this compound was facilitated from E-diamino tri-substituted alkene B as a synthon for the synthesis of A through one-electron oxidation. The E-diamino tri-substituted alkene B was synthesized by the two-electron reduction of N,N'-1,2-propylene-bridged bis-2-phenyl-pyrrolinium cation C. Under two-electron oxidation, alkene B transforms back to cation C involving a double carbocation rearrangement.

A bis-NHC-CAAC dimer derived dicationic diradical.

The isolation of carbon-centered diradicals is always challenging due to synthetic difficulties and their limited stability. Herein we report the synthesis of a trans-1,4-cyclohexylene bridged bis-NHC-CAAC dimer derived thermally stable dicationic diradical. The diradical character of this compound was confirmed by EPR spectroscopy. The variable temperature EPR study suggests the singlet state to be marginally more stable than the triplet state (2J = -5.5 cm-1 (ΔE ST = 0.065 kJ mol-1)). The presence of the trans-1,4-cyclohexylene bridge is instrumental for the successful isolation of this dicationic diradical. Notably, in the case of ethylene or propylene bridged bis-NHC-CAAC dimers, the corresponding dicationic diradicals are transient and rearrange to hydrogen abstracted products.

Mol-ecular structure of fac-[Mo(CO)3(DMSO)3].

The title compound, tri-carbonyl-tris-(dimethyl sulfoxide)-molybdenum, [Mo(C2H6OS)3(CO)3] or fac-[Mo(CO)3(DMSO)3], crystallizes in the triclinic space group P with two mol-ecules in the unit cell. The geometry around the central molybdenum is slightly distorted octa-hedral and the facial isomer is found exclusively. The packing within the crystal is stabilized by three-dimensional non-classical inter-molecular hydrogen-bonding contacts between individual methyl substituents of di-methyl sulfoxide and the oxygen atoms of either another di-methyl sulfoxide or a carbonyl ligand on adjacent complex mol-ecules. The observed bond lengths in the carbonyl ligands and between carbonyl carbon atoms and molybdenum are correlated to the observed FT-IR bands for the carbonyl stretches and compared to respective metrical parameters of related complexes.

Reduction induced S-nucleophilicity in mono-dithiolene molybdenum complexes - in situ generation of sulfonium ligands.

The reduction of a molybdenum monodithiolene complex, [Mo(CO)2(dt)(dppe)], in the presence of dichloromethane leads to the transfer of CH2 to sulfur and respective sulfonium species. Detailed analytical and mechanistical spectroscopic and electrochemical studies reveal the reasons for the unexpected formation and composition of the very unusual resultant complexes to be electronic-energetic in nature.

A multi-method chemometric analysis in spectroelectrochemistry: Case study on molybdenum mono-dithiolene complexes.

Spectroelectrochemical (SEC) analyses combine spectroscopic measurements with electrochemical techniques and can provide deep insight into complex multi-component chemical reaction systems. SEC experiments typically produce large amounts of spectroscopic data. Chemometric techniques are required for the data analysis and aim at extracting the underlying pure component information. Here we analyze spectroelectrochemically gained UV-vis data from five molybdenum mono-dithiolene complexes with changing redox states. SEC enables an electrochemical control of the mixture composition which supports the application of chemometric curve resolution techniques. The factor ambiguity problem is addressed by a multi-method approach combining chemometric tools from the evolving factor analysis (EFA) and from the area of feasible solutions (AFS) methodology in combination with factor duality arguments. EFA enables a subsystem analysis. Two subsystems with three species each are identified, which belong to a reductive and to an oxidative region. A joint species is contained in both regions. A complete pure component decomposition becomes possible in a final step.

Synthesis and reactivity of NHC-coordinated phosphinidene oxide.

Here we report the synthesis of an N-heterocyclic carbene (NHC)-stabilised phosphinidene oxide by the controlled oxygenation of a phosphinidene under ambient conditions. This compound can be further oxygenated to a phosphinidene dioxide. The stoichiometric reduction of a phosphinidene oxide with KC8 resembles the pinacol coupling reaction-the reduction of a carbonyl compound. We also looked at the stoichiometric oxidation of NHC-coordinated phosphinidene, phosphinidene oxide and phosphinidene dioxide with [NO][SbF6].