A tetranuclear arylstibonic acid with an adamantane type structure

Abstract

Oxidative chlorination of ArSbCl2 (1) with SO2Cl2 provided ArSbCl4 (2), the base hydrolysis of which gave rise to the arylstibonic acid (ArSb)4O6(OH)4 (3) having an adamantane type structure. The intramolecularly coordinating substituent Ar = 6-diphenylphosphinoacenaphth-5-yl- modulates the Lewis acidity of 1-3 and prevents extensive aggregation.

The Effect of Donor Additives on the Stability and Structure of 5‐Diphenylphosphinoacenaphth‐6‐yllithium

“…5‐Diphenylphosphinoacenaphth‐6‐yllithium, 5‐Ph 2 P‐Ace‐6‐Li, an important starting material for the synthesis of peri ‐substituted scaffolds was isolated for the first time and fully characterized as the tetranuclear (5‐Ph 2 P‐Ace‐6‐Li) 4 · 4toluene and as the dinuclear (5‐Ph 2 P‐Ace‐6‐Li · OEt 2 ) 2 · toluene by X‐ray crystallography and 7 Li MAS and 31 P MAS NMR spectroscopy. Apart from Et 2 O, other donor solvents/additives including THF, DME, TMEDA, DABCO give rise to rapid decomposition of 5‐Ph 2 P‐Ace‐6‐Li.…”

“…Ever since their discovery about 100 years ago, organolithium compounds rank amongst the most versatile and widely used reagents in organic and organometallic chemistry In this regard, 5‐diphenylphosphinoacenaphth‐6‐yllithium, 5‐Ph 2 P‐Ace‐6‐Li (Scheme ), has been extensively used for the preparation of peri ‐substituted acenaphthyl scaffolds to study the through‐space interactions between the P atom and a variety of main group elements (B, Al, Ga, In, Tl, Si,, Sn, Pb, P, As, Sb,, Bi and Te) as well as transition metals (Au,, Hg, ).…”

Sterically Congested 5-Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

“…In order to quantify the energy associated with the increasing steric congestion, a set of isodesmic reactions was calculated, and two different peri -interaction energies (PIEs) were defined and validated against disubstituted naphthalene isomers. Extending upon our preceding studies, ,,− we carried out topological analyses of the computed electron and pair densities according to the atoms-in-molecules (AIM) and electron localizability indicator (ELI-D) space-partitioning schemes. By definition of surfaces of zero electronic flux, atomic basins and a topological bond path motif are generated within the AIM scheme, which affords the detection of weak to nonbonding interactions and the quantification of charge transfer between atoms or molecular fragments, whereas ELI-D generates basins of paired electrons, which yields the localization/visualization and quantification of core, bonding, and nonbonding electron pairs.…”

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“…[357] A similar compound can also be achieved by treating the C,Pcoordinated Sb complex (dpan)SbCl4 (dpan = 6diphenylphosphinoacenaphth-5-yl) with a basic aqueous solution, yielding [{(dpan)(OH)Sb}4O6] (662). [358] Lanthanide/group 16 adamantane-type clusters. Lanthanides occupying positions within the adamantane-type scaffolds are only known in combination with oxygen in the E position for a number of oxygen centered compounds.…”