A novel bulky bis(4,6-tBu-benzoxazol-2-yl)methane ligand was synthesized in a straightforward three-step synthesis. The corresponding complexes [Li{(4,6-tBu-NCOC H ) CH}THF], [K{η -(4,6-tBu-NCOC H ) CH}] , and [MgCl{(4,6-tBu-NCOC H ) CH}(THF) ] were obtained upon metalation with alkaline or alkaline-earth-metal reagents. Reduction of [MgCl{(4,6-tBu-NCOC H ) CH}(THF) ] with potassium metal or KC led to the formation of the homoleptic compound [Mg{(4,6-tBu-NCOC H ) CH} ]. All compounds were fully characterized. Their solid-state structures as well as their behavior in solution, which was analyzed with the help of advanced NMR spectroscopic techniques, are discussed in detail.

Aggregate formation of organometallic compounds can be straightforwardly observed and interpreted through DOSY molecular weight (MW) estimation. Recently, the power‐law approach and preparation of external calibration curves (ECCs) has propelled the applicability of this DOSY MW estimation. However, effective prediction of MWs of molecules containing heavier elements (e. g. halogenated compounds) has not been sufficiently accounted for. Hence, we introduce specialized ECCs for various halogenated molecules. In an innovative attempt we propose a correction factor for standard ECCs that scales with molecular features to extend considerably the range of molecules that can be investigated by ECC‐DOSY.

A new method, based on slice-selective NMR spectroscopy of inhomogeneous mixtures, is introduced to perform NMR titrations and reaction monitoring in a single experiment. The method was applied to the titration of a lithium salt with 12-crown-4, and to the reaction of nBuLi with N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDTA).

Configurational and conformational characterization of two synthetic β‐amino acid esters comprising an indan motif was achieved by residual dipolar couplings. We further observed that the stability of Q factors upon addition of structural noise substantially facilitates the selection of the “correct” structure. The two analyzed compounds differ by a single methyl group, which leads to a remarkable conformational change.