The synthesis of potassium 6-hydroxy-7-chloro-1,1-dimethyl-3,3-difluorobenzo-1,2,3-siloxaborolate 5b from readily available 4-bromo-2-chlorophenol was developed.
Two covalent organic frameworks comprising Lewis basic P III centers and Lewis acidic boron atoms were prepared by poly-condensation reactions of newly obtained tris(4-diisopropoxyborylphenyl)phosphine with 2,3,6,7,10,11hexahydroxytriphenylene and 2,3,6,7-tetrahydroxy-9,10-dimethylanthracene. Obtained materials exhibit significant sorption of dihydrogen (100 cm 3 g À1 at 1 bar at 77 K), methane (20 cm 3 g À1 at 1 bar at 273 K) and carbon dioxide (50 cm 3 g À1 at 1 bar at 273 K). They were exploited as solidstate ligands for coordination of Pd 0 centers. Alternatively, in a bottom-up approach, boronated phosphine was treated with Pd 2 dba 3 and poly-condensated, yielding hybrid materials where the polymer networks are formed by means of covalent boronate linkages and coordination PÀPd bonds. In addition, the analogous materials based on phosphine oxide were synthesized. The DFT calculations on framework-guest interactions revealed that the behavior of adjacent boron and phosphorus/phosphine oxide centers is reminiscent of that found in Frustrated Lewis Pairs and may improve sorption of selected molecules.
The review covers the chemistry of organoboron heterocycles structurally related to benzoxaboroles where one of the carbon atoms in a boracycle or a fused benzene ring is replaced by a heteroelement such as boron, silicon, tin, nitrogen, phosphorus, or iodine. Related ring expanded systems including those based on naphthalene and biphenyl cores are also described. The information on synthetic methodology as well as the basic structural and physicochemical characteristics of these emerging heterocycles is complemented by a presentation of their potential applications in organic synthesis and medicinal chemistry, the latter aspect being mostly focused on the promising antimicrobial activity of selected compounds.
We have demonstrated that the general approach to phosphine coordination materials, mostly developed for MOF families, can be successfully extended to Covalent Organic Frameworks. Consequently,w eh ave obtained as eries of COFs comprising both Lewis acid boron and Lewis base P III /P=Os ites. These bifunctional COFs showed significant gas sorption ability and can be easily functionalized with metal atoms using both post-synthetic and bottom-up approaches. The DFT calculations on framework-guest interactions revealed that the behavior of adjacent boron and P III /P=Oc enters is reminiscent of that found in Frustrated Lewis Pairs.
Boronate covalent organic frameworks comprising Lewis basic PIII and P=O centers were prepared and showed significant sorption of dihydrogen, methane, and carbon dioxide. In addition, related hybrid materials comprising covalent boronate linkages and coordination P−Pd bonds were obtained. The DFT calculations on framework–guest interactions revealed that the behavior of adjacent boron and PIII/P=O centers is reminiscent of that found in frustrated Lewis pairs. More information can be found in the Full Paper by K. Durka, S. Luliński, et al. on page 12758.
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