Synthesis and Reactivity of a Dialane-Bridged Diradical.

Radicals of the lightest group 13 element, boron, are well established and observed in numerous forms. In contrast to boron, radical chemistry involving the heavier group 13 elements (aluminum, gallium, indium, and thallium) remains largely underexplored, primarily attributed to the formidable synthetic challenges associated with these elements. Herein, we report the synthesis and isolation of planar and twisted conformers of a doubly CAAC (cyclic alkyl(amino)carbene)-radical-substituted dialane. Extensive characterization through spectroscopic analyses and X-ray crystallography confirms their identity, while quantum chemical calculations support their open-shell nature and provide further insights into their electronic structures. The dialane-connected diradicals exhibit high susceptibility to oxidation, as evidenced by electrochemical measurements and reactions with o-chloranil and a variety of organic azides. This study opens a previously uncharted class of dialuminum systems to study, broadening the scope of diradical chemistry and its potential applications.

Stepwise and selective synthesis of chelating, multimetallic and mixed-metal π-diborene complexes.

The reaction of a pyridyl-substituted, doubly Lewis base-stabilised diborene with different amounts of copper(I) precursors led to the formation of the first chelating π-diborene complexes, the first π-diborene complexes in which metals are bound to both faces of the BB bond, and the first mixed-metal π-diborene species.

Tricoordinate Beryllium Radicals and Their Reactivity.

The one-electron reduction of [(CAAC)Be(Dur)Br] (CAAC = cyclic alkyl(amino)carbene, Dur = 2,3,5,6-tetramethylphenyl = duryl) with lithium sand in diethyl ether yields the first neutral, tricoordinate, and moderately stable beryllium radical, [(CAAC)(Et2O)BeDur]• (2-Et2O), which undergoes a facile second one-electron reduction concomitant with the insertion of the beryllium center into the endocyclic C-NCAAC bond and a cyclopropane-forming C-H bond activation of an adjacent methyl group. In situ generation of 2-Et2O and addition of PMe3 yield the stable analogue, [(CAAC)(Me3P)BeDur]• (2-PMe3), which serves as a platform for PMe3-ligand exchange with stronger donors, generating the radicals [(CAAC)LBeDur]• (2-L, L = isocyanides, pyridines, and N-heterocyclic carbenes). X-ray structural analyses show trigonal-planar beryllium centers and strong π backbonding from the metal to the CAAC ligand. The EPR signals of all six isolated [(CAAC)LBeDur]• radicals display significant, albeit small, hyperfine coupling to the 9Be nucleus. DFT calculations show that the spin density is mostly delocalized over the CAAC π framework and, where present, the isocyanide CN moiety, with only a small proportion (3-6%) on the beryllium center. 2-PMe3 proved thermally unstable at 80 °C, first undergoing radical hydrogen abstraction with the solvent, followed by insertion of beryllium into the endocyclic C-NCAAC bond and PMe3 transfer to the former carbene carbon atom. The reactions with diphenyl disulfide and phenyl azide occur at the beryllium center and yield the corresponding Be(II) phenyl sulfide and amino complexes, respectively, the latter concomitant with radical transfer and hydrogen abstraction by the beryllium-bound nitrogen center.

Unlocking Heteroaromatic Ring Systems through Chalcogen Insertion into Boroles.

In this work, we report the reactivity of various annulated borole derivatives toward chalcogen (O, S, and Se) insertion. Among a series of 9-borafluorenes with different boron substituents (Ph, Br, or o-carboranyl) and a mixed thiophene-benzene-fused derivative, only the 9-o-carboranyl-substituted 9-borafluorene yielded the complete set of chalcogen-containing heteroarenes, including the first 1,2-selenaborinine derivative. To evaluate the aromaticity of this heterocyclic analogue of phenanthrene, nucleus-independent chemical shift (NICS) values were computed and compared to those of its lighter group 16 congeners.

Synthesis and Reactivity of Highly Electron-Rich Zerovalent Group 10 Diborabenzene Pogo-Stick Complexes.

A cyclic alkyl(amino)carbene (CAAC)-stabilized 1,4-diborabenzene (DBB, 1) reacts with the group 10 precursor [Ni(CO)4] to yield the DBB pogo-stick complex [(η6-DBB)Ni(CO)] (2) as a dark-green crystalline solid. The IR-spectroscopic and X-ray crystallographic data of 2 highlight the strong π-donor properties of the DBB ligand. The reaction of 1 with [M(nbe)2] (M = Pd, Pt; nbe = norbornene) yields the unique zerovalent heavier group 10 arene pogo-stick complexes [(η6-DBB)M(nbe)] (3-M), isolated as dark-purple and black crystalline solids, respectively. 3-Pd and 3-Pt show strong near-IR (NIR) absorptions at 835 and 904 nm, respectively. Time-dependent density functional theory (TD-DFT) calculations show that these result from the S0→S1 excitation, which corresponds to a transfer of electron density from a metal d orbital aligned with the z direction (dxz or dyz) to a d orbital located in the xy plane (dxy or dx2-y2), with the redshift for 3-Pt resulting from the higher spin-orbit coupling (SOC). In complex 2, electron donation from the nickel center into the carbonyl 2π* orbital destabilizes the DBB···Ni interaction, resulting in an absorption at a higher energy. Complexes 2 and 3-M react with [Fe(CO)5] to yield the doubly CO-bridged M(0)→Fe(0) (M = Ni, Pd, Pt) metal-only Lewis pairs (MOLPs) 4-M as black (M = Ni, Pt) and dark-turquoise (M = Pd) crystalline solids. Furthermore, 3-Pt undergoes oxidative Sn-H addition with Ph3SnH to yield the corresponding Pt(II) stannyl hydride, [(η6-DBB)PtH(SnPh3)] (5).

Boron Insertion into the N≡N Bond of a Tungsten Dinitrogen Complex.

The 1,3-addition of 1,2-diaryl-1,2-dibromodiboranes (B2Br2Ar2) to trans-[W(N2)2(dppe)2] (dppe = κ2-(Ph2PCH2)2), which is accompanied by a Br-Ar substituent exchange between the two boron atoms, is followed by a spontaneous rearrangement of the resulting tungsten diboranyldiazenido complex to a 2-aza-1,3-diboraallenylimido complex displaying a linear, cumulenic B=N=B moiety. This rearrangement involves the splitting of both the B-B and N=N bonds of the N2B2 ligand, formal insertion of a BAr boranediyl moiety into the N=N bond, and coordination of the remaining BArBr boryl moiety to the terminal nitrogen atom. Density functional theory calculations show that the reaction proceeds via a cyclic NB2 intermediate, followed by dissociation into a tungsten nitrido complex and a linear boryliminoborane, which recombine by adduct formation between the nitrido ligand and the electron-deficient iminoborane boron atom. The linear B=N=B moiety also undergoes facile 1,2-addition of Brønsted acids (HY = HOPh, HSPh, and H2NPh) with concomitant Y-Br substituent exchange at the terminal boron atom, yielding cationic (borylamino)borylimido tungsten complexes.

Boroles from alumoles: accessing boroles with alkyl-substituted backbones via transtrielation.

The alumole Cp3tAlC4Et4 (Cp3t = 1,2,4-tris(tert-butyl)cyclopentadienyl) is reported to be capable of transferring its butadiene moiety to aryl(dihalo)boranes to generate boroles through aluminum-boron exchange. The products feature a rare alkyl-substituted backbone, which, as shown in other examples, often leads to dimerization due to insufficient steric protection of the antiaromatic borole ring. Sterically crowded aryl groups bound to the boron atom are shown to prevent dimerization, allowing access to the first monomeric derivatives of this type. Results from UV-vis spectroscopy, electrochemistry, and DFT calculations reveal that the alkyl substituents cause remarkable modifications in the optical and electronic properties of the boroles compared to their perarylated counterparts.

Coinage metal complexes of BN analogues of m-terphenyl ligands.

We report the synthesis of a series of group 11 metal complexes with sterically demanding anionic nitrogen ligands based on the 1,2-azaborinine motif. The ligands, which share structural similarities with m-terphenyls, have been used to stabilize two-coordinate phosphine complexes and dimeric complexes with close contacts between the metal centers. Spectroscopic, crystallographic, and theoretical investigations reveal close parallels to the related m-terphenyl complexes, including metallophilic interactions in the dimers.

Dibenzoberylloles: antiaromatic s-block fluorene analogues.

Among a series of Lewis-base-stabilised antiaromatic dibenzoberylloles (DBBes) the cyclic alkyl(amino)carbene (CAAC) analogue undergoes a complex but highly selective thermal decomposition, involving the breaking and making of four bonds each, which yields a rare beryllium η2-alkene complex. Two-electron reduction of the CAAC-stabilised DBBe analogue yields an aromatic dianion.

Structural Investigation on How Guest Loading of Poly(2-oxazoline)-Based Micelles Affects the Interaction with Simulated Intestinal Fluids.

Drug loading of polymer micelles can have a profound effect on their particle size and morphology as well as their physicochemical properties. In turn, this influences performance in biological environments. For oral delivery of drugs, the intestinal environment is key, and consequently, a thorough structural understanding of what happens at this material-biology interface is required to understand in vivo performance and tailor improved delivery vehicles. In this study, we address this interface in vitro through a detailed structural characterization of the colloidal assemblies of polymeric micelles based on poly(2-oxazolines) with three different guest loadings with the natural product curcumin (17-52 wt %) in fed-state simulated intestinal fluids (FeSSIF). For this, we employ NMR spectroscopy, in particular, 1H NMR, 1H-1H-NOESY, and 1H DOSY experiments complemented by quantum chemical calculations and cryo-TEM measurements. Through this mixture of methods, we identified curcumin-taurocholate interactions as central interaction patterns alongside interactions with the polymer and lipids. Furthermore, curcumin molecules can be exchanged between polymer micelles and bile colloids, an important prerequisite for their uptake. Finally, increased loading of the polymer micelles with curcumin resulted in a larger number of vesicles as taurocholate─through coordination with Cur─is less available to form nanoparticles with the lipids. The loading-dependent behavior found in this study deviates from previous work on a different drug substance highlighting the need for further studies including different drug molecules and polymer types to improve the understanding of events on the molecular level.

Synthesis, Structural Characterization, and Bonding of Molecular Heavier Beryllium Chalcogenides.

The reactions of a cyclic alkyl(amino)carbene (CAAC)-stabilized beryllium radical with E2 Ph2 (E=S, Se, Te) and of a beryllole with HEPh (E=S, Se) yield the corresponding beryllium phenylchalcogenides, including the first structurally authenticated beryllium selenide and telluride complexes. Calculations show that their Be-E bonds are best described by the interaction between the Be+ and E- fragments, with Coulombic forces accounting for ca. 55 % of the attraction and orbital interactions dominated by the σ component.