Related Experiment Video
Updated: Jun 22, 2026

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Selenoether macrocyclic chemistry-syntheses and ligand properties of new small-ring Se(3)- and Se(2)N-donor
William Levason1, Joanna M Manning, Gillian Reid
1School of Chemistry, University of Southampton, Southampton, UKSO17 1BJ.
Abstract:
Simultaneous dropwise addition of thf/EtOH solutions of Se{(CH(2))(3)OTs}(2) and o-C(6)H(4)(CH(2)SeCN)(2) or NCSe(CH(2))(3)SeCN to a suspension of NaBH(4) in thf/EtOH at room temperature yields gram quantities of the 13- and 12-membered triselenoether macrocycles (1) and (2) respectively in high yield. The 11-membered ring (3) is obtained similarly by simultaneous dropwise addition of thf/EtOH solutions of Na(2)[o-C(6)H(4)Se(2)] (itself prepared by NaBH(4) reduction of the polymeric [o-C(6)H(4)Se(2)](n)) and Se{(CH(2))(3)OTs}(2) to a suspension of NaBH(4) in thf/EtOH. The small-ring, potentially tridentate Se(2)N(pyridyl)-donor macrocycles (4) and (5) were obtained in essentially quantitative yield by simultaneous dropwise addition of thf/EtOH solutions of 2,6-bis(bromomethyl)pyridine and either o-C(6)H(4)(CH(2)SeCN)(2) or NCSe(CH(2))(3)SeCN to a suspension of NaBH(4) in thf/EtOH at room temperature. (1)-(5) have been characterised by (1)H, (13)C{(1)H} and (77)Se{(1)H} NMR spectroscopy, EI MS, and for (1) and (4), by X-ray crystal structures. Reaction of PtMe(3)I with one mol. equiv. of L (L = (1)-(5)) in refluxing CHCl(3) gives the ionic complexes [PtMe(3)(L)]I cleanly and in good yield. These were characterised by (1)H, (13)C{(1)H}, (77)Se{(1)H} and (195)Pt NMR spectroscopy, electrospray MS, microanalyses and by crystal structures of [PtMe(3)((1))]I and [PtMe(3)((4))]I, which confirm distorted octahedral coordination at Pt(IV), with fac-tridentate coordination of the macrocycle in all cases, with anionic iodide. The complexes [PtCl(2)(L)] (L = (1)-(3)) were obtained as poorly soluble yellow-orange solids by reaction of PtCl(2) with L in MeCN solution. The d(3) Cr(III) complexes of L (L = (1)-(5)) were obtained by reaction with [CrCl(3)(thf)(3)] in anhydrous CH(2)Cl(2) as distorted octahedral fac-[CrCl(3)(L)], as poorly soluble blue-purple through to green powdered solids, which have been characterised by microanalysis, UV-visible and IR spectroscopy and by their magnetic moments. The properties of these complexes are compared with related chalcogenoether complexes from the literature involving thioether and acyclic selenoether coordination.
Related Concept Videos
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Preparation and Reactions of Sulfides

