Ar igid naphthalenediamine framework has been used to prepare antimony hydrides that feature LUMO shapes and energies similar to those found in secondary boranes.B y exploiting this feature,w ei ntroduce the first examples of uncatalyzed hydrostibination reactions of robust CC, C=C, C = O, and N = Nb onds as new elementary hydrometalation reactions analogous to hydroboration. These results endorse the notion of ad iagonal relationship between the lightest p-block element and the heaviest Group 15 elements and may lead to the conception of novel reaction chemistry.

The reactions of CO 2 with as eries of phosphinoboranes, including R 2 PBpin (R = Ph, tBu;p in = pinacol), R 2 PBMes 2 (R = Ph, tBu;M es = 2,4,6-Me 3 -C 6 H 2 ), and R 2 PBcat (R = Ph, tBu, Mes;c at = catechol)a re described. Although R 2 PBpina nd R 2 PBMes 2 afford products of the form R 2 PCO 2 Bpin (R = Ph 1, tBu 4)a nd R 2 PCO 2 BMes 2 (R = Ph 2, tBu 3), respectively,R 2 PBcat lead to further reactionaffording the diphospha-ureas, (R 2 P) 2 CO (R = Ph 5, tBu 6,M es 7), together with O(Bcat) 2 .C omputational studiesp rovide insight into the mechanism, revealing an intermediate derived from double phosphinoboration of CO 2 .[a] J.Supporting information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.org/10.

Reaction of dihydrogen and the borinium cation salt [Mes2B]­[B­(C6F5)4] gave an arene-stabilized mesityl-borenium cation, which isotopically scrambles HD. Similarly, reaction with triethylsilane gave the diboranium cation [MesB­(μ-H)2(μ-Mes)­BMes]+ featuring three bridge-bonds between two boron centers. Reaction of same (Mes2BH)2 with Brønsted acid also afforded the same diboranium whereas the corresponding reaction with (MesBH2)2 yielded the triboron cation [H2B­(μ-H)­(μ-Mes)­B­(μ-Mes)­(μ-H)­BH2]+.

Tetraarylmethanes and adamantanes are important rigid covalent connectors that play a four-way scaffolding role in molecular and materials chemistry. We report the synthesis of a new tetravalent phosphazaadamantane cage, (PNSiMe 3 ) 4 (NMe) 6 (2), that shows high thermal, air, and redox stability due to its geometry. It nevertheless participates in covalent four-fold functionalization reactions along its periphery. The combination of a robust core and reactive corona makes 2 a convenient inorganic scaffold upon which tetrahedral molecular and macromolecular chemistry can be constructed. This potential is demonstrated by the synthesis of a tetrakis(bis(phosphine)iminium) ion (in compound 3) and the first all P/N poly(phosphazene) network (5).

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