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In this work, an alane, [DNIAlH2] (1) (DNI = 3,3-dimethyl-2-[2-methyl-2-(2,6-diisopropyl-aniline)ethenyl]-3H-indolenine), stabilised by a hybrid ligand was reduced by Jones's Mg(I) ([(MesBDIMg)2]) and Roesky's Al(I) ([DippBDIAl:]). The resulting dialane compound [{DNI(H)Al}2] (2) was characterised using NMR spectroscopy, mass spectrometry, DFT calculations and single-crystal XRD experiments. The reaction of aluminium dihydride [DNIAlH2] (1) with [DippBDIAl:] at high temperatures gives an intramolecular C(sp2)–H bond-activated compound 3. To study the monomeric hybrid ligand-based Al(I), characterisations and computational calculations were performed, which elucidate that compound 5, consisting of two inequivalent aluminium atoms in an Al2CN four-membered ring, resulting from the activation of a carbon–nitrogen bond in the reaction of [DNINa] with [(Cp*Al)4]. [ABSTRACT FROM AUTHOR]

A new NMR method for structural verification and 11B resonance assignment in (car)borane clusters is presented, based on the measurement of 11B residual quadrupolar couplings (RQCs) in a stretched polystyrene (PS) gel. The method was applied to ortho-carborane (B10C2H12), a derivative thereof with reduced symmetry, meta-carborane and decaborane (B10H14). [ABSTRACT FROM AUTHOR]

A new NMR method for the structure elucidation of lithium compounds under solution‐like conditions is presented. It is based on the measurement of 7Li residual quadrupolar couplings (RQCs) in a stretched polystyrene (PS) gel, and comparison to RQCs predicted from crystal or DFT‐derived model structures in combination with alignment tensors derived from one‐bond 1H,13C residual dipolar couplings (RDCs). The method was applied to five lithium model complexes containing monoanionic, bidentate bis(benzoxazole‐2‐yl)methanide, bis(benzothiazole‐2‐yl)methanide and bis(pyridyl)methanide ligands, of which two are first introduced in this work. In agreement with the crystalline state, four complexes are monomeric with Li coordinated fourfold by two additional THF molecules, whereas in one complex bulky tBu groups only provide space for one additional THF molecule. [ABSTRACT FROM AUTHOR]

Two mononuclear ruthenium(II) complexes based on dianionic {N4} ligands and with axial pyridines have been prepared and characterized crystallographically (1) or by 2D NMR spectroscopy using residual dipolar couplings (2). The {N4} ligands provide a constrained equatorial coordination with one large N−Ru−N angle, and additional non‐coordinating N atoms in case of 2. Their redox properties have been investigated (spectro)electrochemically, and their potential to serve as water oxidation catalysts has been probed using cerium ammonium nitrate (CAN) at pH 1.0. Complex 1 undergoes rapid degradation, likely via ligand oxidation, whereas 2 is more rugged and exhibits 80 % efficiency in the CeIV‐driven water oxidation, with a high initial turnover frequency (TOFi) of 3.07×10−2 s−1 (at 100 equiv. CAN). The initial rate of O2 evolution exhibits 1st order dependence on catalyst concentration, suggesting a water nucleophilic attack mechanism. Repeated addition of CAN and control experiments show that high ionic strength conditions (both NO3− and CeIII) significantly decrease the TOF. [ABSTRACT FROM AUTHOR]

The article titled "Front Cover: Synthesis of a Novel Hybrid Ligand System Incorporating Classic Moieties through Acylation of 2,3,3-Trimethylindolenine" explores the synthesis of a new hybrid ligand called "DNI." The ligand combines elements from two existing ligand systems, the BDI (NacNac) and Box (bis(heterocyclo)methane) ligands, to enhance steric demand. The front cover of the journal depicts the conceptual evolution of these ligands, with the DNI ligand represented in the center. The article acknowledges the contribution of Huiqiang Chen in producing the front cover. [Extracted from the article]

In this work, an alane, [DNIAlH 2 ] (1) (DNI = 3,3-dimethyl-2-[2-methyl-2-(2,6-diisopropyl-aniline)ethenyl]-3 H -indolenine), stabilised by a hybrid ligand was reduced by Jones's Mg(I) ([( Mes BDIMg) 2 ]) and Roesky's Al(I) ([ Dipp BDIAl:]). The resulting dialane compound [{DNI(H)Al} 2 ] (2) was characterised using NMR spectroscopy, mass spectrometry, DFT calculations and single-crystal XRD experiments. The reaction of aluminium dihydride [DNIAlH 2 ] (1) with [ Dipp BDIAl:] at high temperatures gives an intramolecular C(sp 2 )-H bond-activated compound 3. To study the monomeric hybrid ligand-based Al(I), characterisations and computational calculations were performed, which elucidate that compound 5, consisting of two inequivalent aluminium atoms in an Al 2 CN four-membered ring, resulting from the activation of a carbon-nitrogen bond in the reaction of [DNINa] with [(Cp*Al) 4 ].

A new NMR method for structural verification and 11 B resonance assignment in (car)borane clusters is presented, based on the measurement of 11 B residual quadrupolar couplings (RQCs) in a stretched polystyrene (PS) gel. The method was applied to ortho -carborane (B 10 C 2 H 12 ), a derivative thereof with reduced symmetry, meta -carborane and decaborane (B 10 H 14 ).

The synthesis of the first inorganic four-membered neutral 2π-aromatic compound 2 is reported. This unique ring has been synthesized from a simple and straightforward reaction of amidinato-silylene with dichlorophenylborane, followed by the reduction with KC 8 in THF. Compound 2 has been fully characterized by single-crystal X-ray diffraction (SC-XRD), NMR spectroscopy, and mass spectrometry. The computational calculations reveal that the Si 2 B 2 ring is a π-delocalized system resulting from the interaction of p π orbital of B and Si-N σ* orbitals having pseudo π symmetry. Compound 2 is the first known example of a neutral planar inorganic analogue of cyclobutenyl dication.

A new NMR method for the structure elucidation of lithium compounds under solution-like conditions is presented. It is based on the measurement of 7 Li residual quadrupolar couplings (RQCs) in a stretched polystyrene (PS) gel, and comparison to RQCs predicted from crystal or DFT-derived model structures in combination with alignment tensors derived from one-bond 1 H, 13 C residual dipolar couplings (RDCs). The method was applied to five lithium model complexes containing monoanionic, bidentate bis(benzoxazole-2-yl)methanide, bis(benzothiazole-2-yl)methanide and bis(pyridyl)methanide ligands, of which two are first introduced in this work. In agreement with the crystalline state, four complexes are monomeric with Li coordinated fourfold by two additional THF molecules, whereas in one complex bulky tBu groups only provide space for one additional THF molecule., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)