Systematic pnictogen variation (P, As, Sb, Bi) in PnMes3–B(C6F5)3 Frustrated Lewis Pairs (FLPs) reveals how both the energy and intensity of charge–transfer excitation can be tuned. Increasing pnicto...

We report the first electronic structure and stability study on two series of trimethylsilyl (triMS) masked pnictogen (Pn) and chalcogen (Ch) anions Pn(triMS)2– and Ch(triMS)− (Pn = P, As, Sb, Bi; Ch = S, Se, Te) as well as AsH2– combining negative ion photoelectron spectroscopy and quantum chemical computations. The Pn and Ch series have exhibited distinct electronic structural patterns due to different numbers of lone pair electrons and triMS ligands. Based on well-defined spectra, precise adiabatic and vertical detachment energies (ADE and VDE) are determined for each of the Pn(triMS)2– and Ch(triMS)− anions, which are all noticeably larger compared to their hydride derivatives, indicating increased electronic stabilities. The magnitude of ADE increments exhibits descending trends from lighter to heavier elements along both Pn and Ch groups, i.e., 0.88, 0.77, 0.53, and 0.44 eV for Pn = P, As, Sb, and Bi and 0.46, 0.31, and 0.15 eV for Ch = S, Se, and Te, respectively. Relativistic multi-reference calculations are carried out to characterize electronic structures of Pn(triMS)2–/Ch(triMS)− anions and corresponding neutral radicals. Only those explicitly including spin–orbit coupling (SOC) effect calculations can reproduce the observed spectral profiles containing heavier Pn/Ch elements, highlighting the important roles of SOC contributions.

Rare examples of alkyl bismuth cations [BiR2(SbF6)] are presented, including cyclopropyl ligands and a bismacyclic structure. The bismuth-centered Lewis acids act as Z-type ligands toward the electro...

New molecular Ga–S-compounds were synthesized following a straightforward and high-yielding alkane elimination pathway. The compounds were characterized using NMR and IR spectroscopy, mass spectrometr...

DFT calculations for the Hg(I) 1,5,9-trimesityldipyrromethene complex, [(MesDPM)Hg]2, predict a 199Hg chemical shift of −648 ppm. The experimental 199Hg NMR spectrum features a singlet close to the p...

Herein, the synthesis, crystal structures, and reactivity studies of triel dihydride complexes with the 1,5,9-trimesityldipyrromethene (MesDPM) ligand is presented.

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...

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...