A triplet stibinidene

Large Spin-Orbit Coupling (SOC) is an intrinsic property of the heavy-elements that directly affects the electronic structures of the compounds. Herein we report the synthesis and characterization of a mono-coordinate bismuthinidene featuring a rigid and bulky ligand. All magnetic measurements (SQUID, NMR) point to a diamagnetic compound. However, multiconfigurational quantum chemical calculations predict the ground state of the compound to be dominated (76%) by a spin-triplet. The apparent diamagnetism is explained by an extremely large SOC induced positive zero-field-splitting of more than 4500 cm −1 that leaves the M S = 0 magnetic sublevel thermally isolated in the electronic ground state.

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“…Note added in proof: During the editing process of this manuscript, a monocoordinate stibinidene appeared in the peer-reviewed literature ( 40 ).…”

Section: Theoretical Analysismentioning

confidence: 99%

Synthesis and isolation of a triplet bismuthinidene with a quenched magnetic response

Pang

Nöthling

Leutzsch

et al. 2023

Science

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“…In our recent study on a triplet bismuthinidene, it was concluded that a remarkable effect of spin‐orbit coupling (SOC) is responsible for its high stability and intriguing magnetic properties [18] . During our investigations, it became obvious that the lighter group 15 analogue, stibinidene, embedded in the same scaffold would aid in understanding of such effect derived from relativity [22] . To this end, we attempted the reduction of M s Fluind‐SbCl 2 ( 1 ) and t Bu‐M s Fluind‐SbBr 2 ( 3 ) with 2.1 equiv.…”

Section: Figurementioning

confidence: 99%

“…[18] During our investigations, it became obvious that the lighter group 15 analogue, stibinidene, embedded in the same scaffold would aid in understanding of such effect derived from relativity. [22] To this end, we attempted the reduction of M s Fluind-SbCl 2 (1) and t Bu-M s Fluind-SbBr 2 (3) with 2.1 equiv. Cp* 2 Co in THF or toluene at ambient temperature under argon (Figure 2A).…”

mentioning

confidence: 99%

Dihydrogen and Ethylene Activation by a Sterically Distorted Distibene

et al. 2023

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Herein, we report the synthesis of a sterically distorted distibene ([4]2) and its transition‐metal‐like reactivity towards two fundamental feedstock chemicals: H2 and ethylene. Although [4]2 exhibits an unusually long Sb=Sb distance and noticeable backbone distortion in the solid state, NMR data suggest that [4]2 remains predominantly as a dimer in solution, even at high temperatures. However, it was proposed that the elusive reactivity of [4]2 toward H2 and ethylene results from reversible dissociation of [4]2 into the transient stibinidene ([4]), which could be observed by NMR spectroscopic techniques.

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“…Recent developments in the field have allowed access to crystalline compounds with monocoordinated antimony and bismuth atoms encumbered by a sterically demanding hydrindacene-based ligand. Tan and Ye obtained a stibinidene [(M s Fluind)Sb] (119) 395 and Cornella and Neese isolated an analogous bismuthinidene [( t Bu-M s Fluind)Bi] (120, Figure 28). 396 Multiconfiguration quantum chemical calculations predict the ground state of 120 to be dominated by a spin triplet.…”

Section: Main Group Based Diradical(oid)s: An Updatementioning

confidence: 99%