Contrary to the general belief that Pd-catalyzed cross-coupling at sites of severe steric hindrance are disfavored, we herein show that the oxidative addition to C À Br ortho to an adamantyl group is as favored as the corresponding adamantyl-free system due to attractive dispersion forces. This enabled the development of a fully selective arylation and alkylation of CÀBr ortho to an adamantyl group, even if challenged with competing non-hindered CÀOTf or CÀCl sites. The method makes use of an air-stable Pd I dimer and enables straightforward access to diversely substituted therapeutically important adamantylarenes in 5-30 min.
Experimental electron-density studies based on high-resolution diffraction experiments allow halogen bonds between heavy halogens to be classified. The topological properties of the electron density in Cl...Cl contacts vary smoothly as a function of the interaction distance. The situation is less straightforward for halogen bonds between iodine and small electronegative nucleophiles, such as nitrogen or oxygen, where the electron density in the bond critical point does not simply increase for shorter distances. The number of successful charge–density studies involving iodine is small, but at least individual examples for three cases have been observed. (a) Very short halogen bonds between electron-rich nucleophiles and heavy halogen atoms resemble three-centre–four-electron bonds, with a rather symmetric heavy halogen and without an appreciable σ hole. (b) For a narrow intermediate range of halogen bonds, the asymmetric electronic situation for the heavy halogen with a pronounced σ hole leads to rather low electron density in the (3,−1) critical point of the halogen bond; the properties of this bond critical point cannot fully describe the nature of the associated interaction. (c) For longer and presumably weaker contacts, the electron density in the halogen bond critical point is only to a minor extent reduced by the presence of the σ hole and hence may be higher than in the aforementioned case. In addition to the electron density and its derived properties, the halogen–carbon bond distance opposite to the σ hole and the Raman frequency for the associated vibration emerge as alternative criteria to gauge the halogen-bond strength. We find exceptionally long C—I distances for tetrafluorodiiodobenzene molecules in cocrystals with short halogen bonds and a significant red shift for their Raman vibrations.
Acetylacetone (2,4-pentanedione) derivatives with N donor substituents represent ditopic ligands with coordination sites of distinctly different Pearson hardness. Deprotonation of the acetylacetone (Hacac) moiety leads to O,O′ chelating monoanionic (acac) ligands suitable for coordination to hard cations. The softer N donor site(s) preferably act as nucleophiles towards softer partners. When the organic molecules are employed as linkers and coordinate via either site, they are often selective and allow to synthesize well-ordered heterometallic solids. This review addresses the derivatives of 17 pentanediones with nitrile, pyridyl and pyrazolyl moieties as N donor substituents, with an emphasis on structurally characterized compounds. Depending on the N donor substituents and the cations, O,O′ or N coordination will dominate. The nitrile-substituted compounds essentially behave as acetylacetones; they may easily O,O′ coordinate to a wide range of cations whereas N coordination is limited to AgI, CuI or, in the case of less soft cations, to longer and presumably weaker contacts, e.g. to the more distant sites in Jahn–Teller distorted CuII. In contrast, pyridyl-substituted pentanediones act as N donor ligands, regardless whether their (H)acac site is chelating a cation or not. The still scarcely explored pyrazolyl derivative shows the most complex coordination pattern: it may be deprotonated both at the acetylacetone and the pyrazol site, the latter affording N,N′ bridging ligands. In addition to N donor nucleophilicity, the distance between the alternative coordination sites and their mutual orientation are relevant for crystal engineering applications.
Illustration of the synthetic procedure of N-CNDs and N-CDs-based bifunctional fluorescence nanoprobe for the detection of VB12 and Co2+ and bioimaging of A549 cell and zebrafish.
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