Tricyclic tin(iv) cages: synthetic aspects and intriguing features of stannatranes and pseudostannatranes

Abstract

This perspective summarizes various synthetic routes of stannatranes and pseudostannatranes along with their interesting features, such as appearance of satellites in their NMR spectra, cluster formation upon hydrolysis and exchange reactions.

Mononuclear Pseudostannatranes Possessing Unsymmetrical [4.4.3.01,5]Tridecane Cage: Experimental and Theoretical Aspects of Reverse Kocheshkov Reaction in Phenyl Pseudostannatrane

“…The remaining positions were occupied by two chloro groups to form a distorted octahedral geometry. In most of the previous reports, Sn acquires hexacoordination by coordinating reactive species present in the reaction mixture or via additional reactive groups of the ligand. , A similar trend is observed in the cases of 1 a , 1 b , 2 a , and 2 b where hexacoordination is acquired by coordinating a solvent molecule (methanol/water) in the sixth position. This type of behavior was also observed in one of our earlier reports on pseudostannatrane [NEt 3 ]­[(N­{CH 2 (2-Me-4-Me-C 6 H 2 O)} 3 )­SnCl 2 ] which was isolated as an ionic product .…”

“…Over recent years, there has been growing interest in the synthesis and structural investigation of tin­(IV) tricyclic compounds having N → Sn transannular interactions. − Among the fused organotin tricycles, molecules having five-membered rings with a [3.3.3.0 1,5 ]­undecane cage are termed “stannatranes,” while molecules containing rings other than five-membered arms are named “pseudostannatranes.” ,− These structures are distinguished by their cage-like structure inclusive of right- or left-handed (Δ and Λ) propeller type geometry and an intramolecular N → Sn bond. − Various stannatranes with general formula N­(CH 2 CH 2 X) 3 SnR (where X = O, S, NMe, CH 2 ; R = alkyl/aryl) and N­{CH 2 C­(O)­X} 3 SnR (where X = O or NMe) have been reported in the past. ,− Their popularity has led to the syntheses of organic compounds and drug carbapenem from N­(CH 2 CH 2 CH 2 ) 3 SnR due to selective reactivity of the Sn–R bond. − In addition, purely inorganic (lacking Sn–C bond) stannatranes are also known and have been recently reported by Jurkschat et al − ,, On the contrary, known pseudostannatranes have unsymmetrical [4.3.3.0 1,5 ]­dodecane and [4.4.3.0 1,5 ]­tridecane cages with oligomeric structures formed via Sn–O bridges and a symmetrical [4.4.4.0 1,6 ]­tetradecane cage as a mononuclear entity. ,, To the best of our knowledge, pseudostannatranes possessing a [4.4.3.0 1,5 ]­tridecane cage as mononuclear entities have not been reported yet.…”

Nanopalladium-Decorated Sn-Na MOF Catalyst for Upgrading Biosugars to 5-Hydroxymethylfurfural in an Aqueous Medium

“…26−28 The developed catalyst consists of a composite of nanopalladium and the Sn/Na heterobimetallic metal−organic framework (Sn-Na MOF). Single-crystal X-ray diffraction reveals the construction of the Sn-Na MOF from nitrilotriacetic acidderived stannatranone cages 29,30 by interconnected pentacoordinated and heptacoordinated Na bridges. The spectroscopic, crystallographic, and microscopic techniques confirmed the uniform dispersion of nanopalladium over the surface of Sn-Na MOF to generate the Pd NPs/Sn-Na MOF.…”

“…The recent advancement in the use of metal-bound water molecules as an intrinsic proton source has amplified the curiosity about using palladium nanoparticles for the current work because Pd nanoparticles provide a large surface area along with the excellent capacity to adsorb water on the surface. − The developed catalyst consists of a composite of nanopalladium and the Sn/Na heterobimetallic metal–organic framework (Sn-Na MOF). Single-crystal X-ray diffraction reveals the construction of the Sn-Na MOF from nitrilotriacetic acid-derived stannatranone cages , by interconnected pentacoordinated and heptacoordinated Na bridges. The spectroscopic, crystallographic, and microscopic techniques confirmed the uniform dispersion of nanopalladium over the surface of Sn-Na MOF to generate the Pd NPs/Sn-Na MOF.…”

3-Aminopropylsilatrane and Its Derivatives: A Variety of Applications

“…Atranes are well-known and very interesting elemental/organometallic derivatives of amino alcohols, in particular trialkanolamines (see Refs. [ 1 , 2 , 3 , 4 , 5 , 6 ] and literature cited therein). Historically, the first atranes were «silatranes», which were synthesized by the transesterification of trialkoxysilanes with triethanolamine or triisopropanolamine ( Scheme 1 ) [ 7 , 8 ].…”