Recent Advances in Rare‐Earth Polypnictides

Abstract

The polypnictide complexes of rare earth cations have drawn the attention of the scientific community for their uncommon bonding modes and potential applications. Herein, we present a systematic and comprehensive summary on recent advances in the field of rare earth polypnictides, focusing on their synthesis, structures, and reactivities. The structural stabilizing effects imposed by the electropositive rare earth cations as well as the reducing capability of rare earth precursors in the synthesis of these polypnictide complexes are described in this review. We also disscuss in detail the bonding interactions and coordination modes between rare earth cations and polypnictide clusters as well as the similarities and the peculiarity of some structures.

f-Element heavy pnictogen chemistry

“…The past few decades have seen significant progresses in f-element phosphorus chemistry, with many novel f-element phosphorus motifs isolated and investigated. 20,24–29 The neutral, soft phosphine donor tends to form weak dative bonding interactions to hard f-element metal ions, though this can be overcome by incorporating P-donor centres into polydentate ligands as demonstrated separately by Fryzuk and Lu, 32–34 and such complexes were reviewed previously, so these compounds are not included here. 20,26,32–34 This section discusses recent advances in f-element complexes containing phosphide/phosphanide, phosphorin, phosphinidiide/phosphinidene, phosphido, and inorganic polyphosphorus ligands.…”

“…This in turn could benefit the development of new synthetic methods, ligand design, catalytic transformations, and materials precursors. Reflecting the growing nature of this field, there have been a number of excellent but very general or ligand-specific review articles and book chapters covering the historical developments of some of the subtopics, 20,24–29 but recent developments justify a broad but detailed review specifically focussed on this topic.…”

“…We aim to highlight the major advances involving all heavy pnictogen ligand types, with the exception of phospholyl and arsolyl ligands, which were reviewed in 2021, 30 and (OCE) − (E = P, As) ligands, which were reviewed in 2019 and are normally O-bound unless the E centre decisively directs the chemistry; 31 several other previous reviews have separately covered the ligand classes that comprise this review. 20,[24][25][26][27][28][29] Here we present current challenges to inspire researchers and focus and guide future efforts of the eld to develop f-element heavy pnictogen chemistry more rapidly in the future. In this review, we include the group 3 elements scandium, yttrium, and lanthanum under the heading of lanthanide sections for convenience.…”

Transfer of polyantimony units

“…1,2 Especially for phosphorus and arsenic, a large variety of examples have been synthesized so far, usually by employing white phosphorus or yellow arsenic in the reaction with transition metal or main group compounds. [3][4][5][6] In contrast, the number of polyantimony ligand complexes is very limited and, therefore, their chemistry was far less investigated. 7 Reasons for this can be attributed to various challenges such as the sensitivity of antimony-containing compounds towards light, the weak Sb-Sb bonding 8 and especially the lack of suitable antimony sources.…”

“…Recently, the chemistry of the polyantimony main group compounds has experienced a revival 5,19 especially by the introduction of the nacnac ligand in combination with Mg and Ga ( i.e. LMg and LGa) in this field.…”