Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C-C bond cleavage.

The cleavage and formation of carbon-carbon bonds have emerged as powerful tools for structural modifications in organic synthesis. Although transition-metal-catalyzed decarbonylation of unstrained diaryl ketones provides a viable protocol to construct biaryl structures, the use of expensive catalyst and high temperature (>140 oC) have greatly limited their universal applicability. Moreover, the direct activation of two inert C - C bonds in diaryl ketones without the assistance of metal catalyst has been a great challenge due to the inherent stability of C - C bonds (nonpolar, thermo-dynamically stable, and kinetically inert). Here we report an efficient light-driven transition-metal-free strategy for decarbonylation of unstrained diaryl ketones to construct biaryl compounds through dual inert C - C bonds cleavage. This reaction featured mild reaction conditions, easy-to-handle reactants and reagents, and excellent functional groups tolerance. The mechanistic investigation and DFT calculation suggest that this strategy proceeds through the formation of dioxy radical intermediate via a single-electron-transfer (SET) process between photo-excited diaryl ketone and DBU mediated by DMSO, followed by removal of CO2 to construct biaryl compounds.

Direct deoxygenative borylation of carboxylic acids.

Carboxylic acids are readily available, structurally diverse and shelf-stable; therefore, converting them to the isoelectronic boronic acids, which play pivotal roles in different settings, would be highly enabling. In contrast to the well-recognised decarboxylative borylation, the chemical space of carboxylic-to-boronic acid transformation via deoxygenation remains underexplored due to the thermodynamic and kinetic inertness of carboxylic C-O bonds. Herein, we report a deoxygenative borylation reaction of free carboxylic acids or their sodium salts to synthesise alkylboronates under metal-free conditions. Promoted by a uniquely Lewis acidic and strongly reducing diboron reagent, bis(catecholato)diboron (B2cat2), a library of aromatic carboxylic acids are converted to the benzylboronates. By leveraging the same borylative manifold, a facile triboration process with aliphatic carboxylic acids is also realised, diversifying the pool of available 1,1,2-alkyl(trisboronates) that were otherwise difficult to access. Detailed mechanistic studies reveal a stepwise C-O cleavage profile, which could inspire and encourage future endeavours on more appealing reductive functionalisation of oxygenated feedstocks.

Understanding Terminal versus Bridging End-on N2 Coordination in Transition Metal Complexes.

Terminal and bridging end-on coordination of N2 to transition metal complexes offer possibilities for distinct pathways in ammonia synthesis and N2 functionalization. Here we elucidate the fundamental factors controlling the two binding modes and determining which is favored for a given metal-ligand system, using both quantitative density functional theory (DFT) and qualitative molecular orbital (MO) analyses. The Gibbs free energy for converting two terminal MN2 complexes into a bridging MNNM complex and a free N2 molecule (2ΔGeq°) is examined through systematic variations of the metal and ligands; values of ΔGeq° range between +9.1 and -24.0 kcal/mol per M-N2 bond. We propose a model that accounts for these broad variations by assigning a fixed π-bond order (BOπ) to the triatomic terminal MNN moiety that is equal to that of the free N2 molecule, and a variable BOπ to the bridging complexes based on the character (bonding or antibonding) and occupancy of the π-MOs in the tetratomic MNNM core. When the conversion from terminal to bridging coordination and free N2 is associated with an increase in the number of π-bonds (ΔBOeqπ > 0), the bridging mode is greatly favored; this condition is satisfied when each metal provides 1, 2, or 3 electrons to the π-MOs of the MNNM core. When each metal in the bridging complex provides 4 electrons to the MNNM π-MOs, ΔBOeqπ = 0; the equilibrium in this case is approximately ergoneutral and the direction can be shifted by dispersion interactions.

H2 Addition to Pincer Iridium Complexes Yielding trans-Dihydride Products: Unexpected Correlations of Bond Strength with Bond Length and Vibrational Frequencies.

R4PONOP-Ir-Me (R1) and R4POCOP-Ir-CO (R2), R = tBu or iPr, are known to undergo acid-catalyzed oxidative addition of H2 that yields octahedral products with two hydrides in a trans-configuration. We use density functional theory to study the free energies (Δ Gtrans) and equilibrium isotope effects (EIEtrans) for H2/D2 addition to R1, R2, and related complexes for R = tBu, iPr, and Me. For a given R, reaction of R1 is ∼5 kcal/mol more exergonic than R2. For a given subclass of complexes, Δ Gtrans is more exergonic for the smaller R. The computed values of Δ Gtrans vary between +5.1 and -17.4 kcal/mol. EIEtrans varies between 0.78 and 1.22. Counterintuitively, it is the less-exergonic reactions that afford products with shorter Ir-H bonds, greater symmetric and asymmetric trans-Ir-(H)2 stretching vibrational frequencies, and more inverse EIEtrans. This disparity is amplified in Me4PONOP-Os-CO, where Δ Gtrans is -35.2 kcal/mol, yet the Os-H bonds are long, and the Os-H vibrational frequencies are low as compared with the Ir-H bonds, and EIEtrans is high (1.20). Attempts are made to account for the inverted bond strength-bond length correlation based on the hydricity of the products and the total negative charge on the trans-Ir(H)2 unit as computed using the Quantum Theory of Atoms in Molecules.