Low-valent cadmium compounds have remained largely unexplored as electron reservoirs, with no precedent for their use in reduction or bond activation chemistry. Here, we address this gap by integratin...

Nature Communications - Although uranium-nitrogen multiple bonding is well developed, there are far fewer uranium-phosphorus and -arsenic multiple bonds, and none for antimony, even in...

Nature Communications - Although uranium-nitrogen multiple bonding is well developed, there are far fewer uranium-phosphorus and -arsenic multiple bonds, and none for antimony, even in...

Higher homologues of the well-known BODIPY dyes for boron, aluminum, gallium, and indium are described. These have been obtained with the halogen substituents chlorine, bromine, and iodine and as mix....

Nitrenes (R–N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity of this important class of transient intermediates has been attributed to their electronic structures, particularly the accessibility of triplet vs singlet states. In contrast, electronic structure trends along the heavier pnictinidene analogues (R–Pn; Pn = P–Bi) are much less systematically explored. We here report the synthesis of a series of metallodipnictenes, {M–Pn═Pn–M} (M = PdII, PtII; Pn = P, As, Sb, Bi) and the characterization of the transient metallopnictinidene intermediates, {M–Pn} for Pn = P, As, Sb. Structural, spectroscopic, and computational analysis revealed spin triplet ground states for the metallopnictinidenes with characteristic electronic structure trends along the series. In comparison to the nitrene, the heavier pnictinidenes exhibit lower-lying ground state SOMOs and singlet excited states, thus suggesting increased electrophilic reactivity. Furthermore, the splitting of the triplet magnetic microstates is beyond the phosphinidenes {M–P} dominated by heavy pnictogen atom induced spin–orbit coupling.

Although two examples of σ-bonded trans-bent [RSbSbR]•– (R = bulky organo- or Ga-groups) that formally contain the Sb2•3– radical trianion moiety are known in p-block chemistry, d- or f-element Sb2•3–...

In this work we investigated the Lewis acid-base properties of potassium dihydrogenpnictogenides and potassium bis(trimethylsilyl)pnictogenides towards different trialkyl trieles (Triel=B−In) and BH3...