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The 1,3-bromoboration of [W(N2)2(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane) with B2Br4(SMe2)2 in the presence of various Lewis bases L yields diboranyldiazenido complexes, with L coordinating either at the terminal or internal boron atom. The 2 : 1 reaction of [W(N2)2(dppe)2] and B2Br4(SMe2)2 yields a 1,2-bis(diazenido)diborane-bridged ditungsten complex with a fully planar π-conjugated BrWN2B2Br2N2WBr core. [ABSTRACT FROM AUTHOR]

The first examples of Lewis base adducts of the parent boraphosphaketene (H2B‐PCO) and their cyclodimers are prepared. One of these adducts is shown to undergo mild decarbonylation and phosphinidene insertion into a B−C bond of a borole, forming very rare examples of 1,2‐phosphaborinines, B/P isosteres of benzene. The strong donor properties of these 1,2‐phosphaborinines are confirmed by the synthesis of their π complexes with the Group 6 metals. [ABSTRACT FROM AUTHOR]

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The 1,3-bromoboration of [W(N2)2(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane) with B2Br4(SMe2)2 in the presence of various Lewis bases L yields diboranyldiazenido complexes, with L coordinating either at the terminal or internal boron atom. The 2 : 1 reaction of [W(N2)2(dppe)2] and B2Br4(SMe2)2 yields a 1,2-bis(diazenido)diborane-bridged ditungsten complex with a fully planar π-conjugated BrWN2B2Br2N2WBr core. [ABSTRACT FROM AUTHOR]

The reactions of a cyclic alkyl(amino)carbene (CAAC)-stabilized beryllium radical with E 2 Ph 2 (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., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

We report a detailed computational and experimental study of the fixation and reductive coupling of dinitrogen with low-valent boron compounds. Consistent with our mechanistic findings, the selectivity toward nitrogen fixation or coupling can be controlled through either steric bulk or the reaction conditions, allowing for the on-demand synthesis of nitrogen chains. The electronic structure and intriguing magnetic properties of intermediates and products of the reaction of dinitrogen with borylenes are also elucidated using high-level computational approaches.

The reaction of a cyclic alkyl(amino)carbene (CAAC)-stabilized thiazaborolo[5,4-d]thiazaborole (TzbTzb) with strong Brønsted acids, such as HCl, HOTf (Tf=O 2 SCF 3 ) and [H(OEt 2 ) 2 ][BAr F 4 ] (Ar F =3,5-(CF 3 ) 2 C 6 H 3 ), results in the protonation of both TzbTzb nitrogen atoms. In each case X-ray crystallographic data show coordination of the counteranions (Cl - , OTf - , BAr F 4 - ) or solvent molecules (OEt 2 ) to the doubly protonated fused heterocycle via hydrogen-bonding interactions, the strength of which strongly influences the 1 H NMR shift of the NH protons, enabling tuning of both the visible (yellow to red) and fluorescence (green to red) colors of these salts. DFT calculations reveal that the hydrogen bonding of the counteranion or solvent to the protonated nitrogen centers affects the intramolecular TzbTzb-to-CAAC charge transfer character involved in the S 0 →S 1 transition, ultimately enabling fine-tuning of their absorption and emission spectral features., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The 1,3-bromoboration of [W(N 2 ) 2 (dppe) 2 ] (dppe = 1,2-bis(diphenylphosphino)ethane) with B 2 Br 4 (SMe 2 ) 2 in the presence of various Lewis bases L yields diboranyldiazenido complexes, with L coordinating either at the terminal or internal boron atom. The 2 : 1 reaction of [W(N 2 ) 2 (dppe) 2 ] and B 2 Br 4 (SMe 2 ) 2 yields a 1,2-bis(diazenido)diborane-bridged ditungsten complex with a fully planar π-conjugated BrWN 2 B 2 Br 2 N 2 WBr core.

The reduction of a cyclic alkyl(amino)carbene (CAAC)-stabilized organoberyllium chloride yields the first neutral beryllium radical, which was characterized by EPR, IR, and UV/Vis spectroscopy, X-ray crystallography, and DFT calculations., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Cyclic alkyl(amino)carbene-stabilized (cyano)hydroboryl anions were synthesized by deprotonation of (cyano)dihydroborane precursors. While they display boron-centered nucleophilic reactivity towards organohalides, generating fully unsymmetrically substituted cyano(hydro)organoboranes, they show cyano-nitrogen-centered nucleophilic reactivity towards haloboranes, resulting in the formation of hitherto unknown linear 2-aza-1,4-diborabutatrienes., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The first examples of Lewis base adducts of the parent boraphosphaketene (H 2 B-PCO) and their cyclodimers are prepared. One of these adducts is shown to undergo mild decarbonylation and phosphinidene insertion into a B-C bond of a borole, forming very rare examples of 1,2-phosphaborinines, B/P isosteres of benzene. The strong donor properties of these 1,2-phosphaborinines are confirmed by the synthesis of their π complexes with the Group 6 metals., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Dihalodiboranes(4) react with a N-heterocyclic silylene (NHSi) to generate NHSi adducts of 1-aryl-2-silyl-1,2-diboraindanes, as was confirmed by X-ray crystallography, featuring the functionalization of both B-X (X=halogen) bonds and a sp 3 - or sp 2 -C-H bond under mild conditions. Coordination of a third NHSi to the proposed 1,1-diaryl-2,2-disilyldiborane(4) intermediates, generated by a twofold B-X insertion, may be crucial for the C-H borylation that leads to the final products. Notably, our results demonstrate the first C-H borylation with a strong B-F bond activated by silylene insertion., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)