Boron bis-(4-methylbenzoxazol-2-yl)-methanide complexes.

Boron compounds have attracted the attention of chemists because of their unique catalytic properties and potential wider material applications. Although group 13 metal compounds, which are based on the bis-(benzoxazol-2-yl)-methane system (Box, ({NCOC6H4}2CH2)), have been reported in the last several years, boron containing Box compounds were still missing. Now we report their successful syntheses and spectroscopic characterisation in this work. The borane compound [({NCOC6H3}2CH)BH2] (1) and haloboranes [({NCOC6H3}2CH)BF2] (2), [({NCOC6H3}2CH)BCl2] (3) and [({NCOC6H3}2CH)BBr2] (4) were characterised in the solid state by single crystal X-ray diffraction and in solution by NMR techniques. In addition, the fluorescence properties of compounds 1-4 are communicated.

Multinuclear Residual Quadrupolar Couplings for Structure and Assignment.

Most stable isotopes have a nuclear spin >1/2, but the quadrupole interaction poses challenge on their detection by nuclear magnetic resonance (NMR). On the other hand, the quadrupole interaction is a rich source of structural information that may be exploited for solution NMR in the form of residual quadrupolar couplings (RQCs) of weakly oriented samples. While 2H RQCs are now well established for structure verification and enantiomeric discrimination of organic molecules, we will in this article highlight some recent work on RQCs of other nuclei (especially 7Li and 11B).

A Neutral Planar Four-Membered Si2B2 2π-Aromatic Ring.

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 KC8 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 Si2B2 ring is a π-delocalized system resulting from the interaction of pπ 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.

Resonance and structural assignment in (car)borane clusters using 11B residual quadrupolar couplings.

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).

Structure Elucidation of Lithium Compounds Using 7 Li Residual Quadrupolar Couplings.

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.

Synthesis of Fluorescent Jasplakinolide Analogues for Live-Cell STED Microscopy of Actin.

The nanometer thickness of filaments and the dynamic behavior of actin-a protein playing a crucial role in cellular function and motility-make it attractive for observation with super-resolution optical microscopy. We developed the solution-phase synthesis of des-bromo-des-methyl-jasplakinolide-lysine, used as the "recognition unit" (ligand) for F-actin in living cells. The first amino acid-Fmoc-O-TIPS-ß-tyrosine-was prepared in 78% yield (two steps in one pot). The new solution-phase synthesis involves 2-phenylisopropyl protection of the carboxyl group and does not require excesses of commercially unavailable amino acids. The overall yield of the target intermediate obtained in nine steps is about 8%. The 2-phenylisopropyl group can be cleaved from carboxyl with 2-3% (v/v) of TFA in acetonitrile (0-10 °C), without affecting TIPS protection of the phenolic hydroxyl in ß-tyrosine and N-Boc protection in lysine. Des-bromo-des-methyl-jasplakinolide-lysine was coupled with red-emitting fluorescent dyes 580CP and 610CP (via 6-aminohexanoate linker). Actin in living cells was labeled with 580CP and 610CP probes, and the optical resolution measured as full width at half-maximum of line profiles across actin fibers was found to be 300-400 nm and 100 nm under confocal and STED conditions, respectively. The solution-phase synthesis of des-bromo-des-methyl-jasplakinolide-lysine opens a way to better fluorescent probe perspective for actin imaging.