The Anhydride Route to Group 15/16 Ligands in Oligomeric and Polymeric Environments: From Metal Complexes to Supraionic Chemistry

Abstract

The aim of this paper is to introduce a synthetic concept suitable for the preparation of a broad variety of compounds. The so-called anhydride route (in this article the term anhydride is used for compounds derived from corresponding acids by formal loss of H2O, H2S and H2Se) has so far led to a range of unusual Group 15/16 ligands in oligomeric and polymeric environments. Commonly, reactions of neutral precursor molecules, for example, [{RP(S)(mu-S)}2] (R=4-anisyl) Lawesson's reagent or [{PhP(Se)(mu-Se)}2] Woollins's reagent and metal salts are performed to result in novel coordination compounds in which ligands and metal atoms form coordination oligomers and polymers. An attempt is made to relate the outcome of the investigations to the type of metal used. By relating the strength of ionic interactions, which correspond to metal-donor distances, to phenomena observed in the solid-state structures, an aspect of supraionic chemistry is described. Chemistry of and beyond novel Group 15/16 anions is further discussed using a novel approach in coordination chemistry where the chemical nature of ligands is unknown prior to the experiment despite the use of a range of similar starting materials.

Novel Five‐ to Ten‐Membered Organoselenium Heterocycles from the Selenation of Aromatic Diols

“…The X-ray structures of 1, 2 and 4 (Figures 1, 2, and 3) confirm the presence of the five-, and seven-membered rings. (14), O(1)-P(1)-Se (2) 105.05 (10), C(6)-P(1)-Se (2) 109.42 (14), Se(1)-P(1)-Se(2) 106.52 (5) The structures of 5 (which co-crystallised with one molecule of dichloromethane), 7, 9, and 10 (which crystallised with two crystallographically independent molecules and a half of molecule of dichloromethane in the asymmetric unit) are illustrated in Figures 4,5,6,and 7. The two phenyl rings attached to phosphorus atoms are almost parallel and, in contrast to previous structures, in both 1 and 2 the exocyclic P=Se groups are almost coplanar with the P-Se-P backbone [the Se=P···P=Se plane is inclined by only 22.96(3) and 21.99(1)°with respect to the P-Se-P www.eurjoc.org plane in 1 and 2, respectively].…”

“…2,4-Bis(phenyl)-1,3-diselenadiphosphetane 2,4-diselenide (WR) has less unpleasant chemical properties and can be prepared readily and handled easily. [6,7] As part of our studies aimed into the reactivity of WR towards different organic substrates, herein, we report the preparation of a series of novel five-to ten-membered phos-Scheme 1. [6,7] As part of our studies aimed into the reactivity of WR towards different organic substrates, herein, we report the preparation of a series of novel five-to ten-membered phos-Scheme 1.…”

Cleavage of P–S bonds and oxygenation by a trinuclear iron carboxylate: Synthesis and structures of iron clusters containing group 15/16 anions

“…9 Whilst the final goal of these investigations is to functionalize and address biomolecules at particular domains via the attachment of metal-containing clusters, a short-term aim is simply to explore new synthetic routes to metal complexes containing P-chalcogen and mixed O-Pchalcogen anions. [10][11][12][13][14][15][16][17][18] These may provide a better understanding of interactions between S-functionalized DNA with metalcontaining clusters. In nature phosphorothioation, whereby a P-O group is transformed to a P-S group, is carried out by bacterial gene clusters on the DNA backbone.…”

“…In previous investigations we described a number approaches, where chalcogen atoms in thio-and selenophosphinic acid anhydrides 20-22 were replaced with oxygen. [12][13][14][15][16] This can be done by hydrolysis, alcoholysis or by chemical transformations of metal carboxylates and Scheme 1 shows recently prepared examples of chalcogen-P-O anions. [12][13][14][15][16] In this work, we were looking for metal-containing starting materials, which may be useful for similar preparations magnet chemistry that may serve this purpose are the carboxylate salts of iron.…”

“…[12][13][14][15][16] This can be done by hydrolysis, alcoholysis or by chemical transformations of metal carboxylates and Scheme 1 shows recently prepared examples of chalcogen-P-O anions. [12][13][14][15][16] In this work, we were looking for metal-containing starting materials, which may be useful for similar preparations magnet chemistry that may serve this purpose are the carboxylate salts of iron. It turned out that the nature of the crystalline products that can be isolated from these reactions depends on the stoichiometric ratio of the starting materials employed (Scheme 2).…”