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Flexible ambiphilic ligand scaffolds have garnered attention in catalysis due to their ability to adopt multiple binding orientations. Recently, several platinum group metal complexes featuring the flexible, ambiphilic b-phosphinoethylborane ligand were reported in the literature; however, the impact of primary coordination sphere ligands and solvent on the properties of the Lewis acidic borane moiety remain underexplored. Rhodium and iridium complexes ligated by 9-borabicyclo[3.3.1]nonanyl-based b- diphenylphosphinoethylborane were studied using a combination of crystallography and 11B NMR spectroscopy. The studies revealed that both the primary coordination sphere and solvent had an impact on the formation of Lewis acid–base adducts. Specifically, inner-sphere Lewis pair formation was dependent on the nature of the X-type ligand bound to the metal center. Similar dependencies were identified with solvents in which Lewis acid interaction was found to correlate with solvent donor number.more » « lessFree, publicly-accessible full text available July 30, 2026
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A unique class of β-boron-functionalized non-steroidal anti-inflammatory compound (pinB-NSAID) was previously synthesized via copper-catalyzed 1,2-difunctionalization of the respective vinyl arene with CO2 and B2pin2 reagents. Here, pinacolylboron-functionalized ibuprofen (pinB-ibuprofen) was used as a model substrate to develop the conditions for pinacol deprotection and subsequent boron functionalization. Initial pinacol-boronic ester deprotection was achieved by transesterification with diethanolamine (DEA) from the boralactonate organic salt. The resulting DEA boronate adopts a spirocyclic boralactonate structure rather than a diazaborocane–DABO boronate structure. The subsequent acid-mediated hydrolysis of DEA and transesterification/transamination provided a diverse scope of new boron-containing ibuprofen derivatives.more » « less
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null (Ed.)Photolysis of ( Me PMP Me ) 2 ZrBn 2 ( Me PMP Me = 3,5-dimethyl-2-(2-pyridyl)pyrrolide) in the presence of diphenylacetylene yields the first η 4 -cyclobutadienyl zirconium complex, ( Me PMP Me ) 2 Zr(η 4 -C 4 Ph 4 ), through formal [2+2] cycloaddition of two alkynes at a putative low-valent zirconium intermediate. This unique reactivity expands the scope of alkyne coupling reactions at low-valent zirconium centers that traditionally produce zirconacyclopentadienes.more » « less
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Two dinuclear lanthanide complexes (Gd and Dy) were prepared and characterized by X-ray, magnetic and computational methods. The Dy analogue shows SMM behavior with an energy barrier of 98.4 K in the absence of an applied dc field. Theoretical calculations were performed on model complexes which support the hypothesis that the energy barrier will increase if the soft-donor atoms S and Se are used in lieu of an O donor.more » « less
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A new cyclic molecule incorporating [Mo III (CN) 7 ] 4− has been characterized by single crystal X-ray methods, SQUID magnetometry and theoretical calculations. The wheel molecule [Mo III (CN) 7 ] 6 [Ni(L)] 12 (H 2 O) 6 exhibits ferromagnetic Mo–Ni coupling which did not exist for the previously reported octacyanometallate analogue [Mo IV (CN) 8 ] 6 [Ni(L)] 12 (H 2 O) 6 . These results indicate that known supramolecular architectures incorporating octacyanometallates can be used as platforms for making new molecules incorporating seven-coordinate cyanide precursors.more » « less
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