Ion-exchangeable cobalt polysulfide chalcogel.

We present a promising approach in synthetic chalcogel chemistry that is extendable to a broad variety of inorganic spacers. Polychalcogenide aerogels with ion-exchange properties are demonstrated in cobalt polysulfide. The new materials show a broad range of pore sizes and high surface area of 483 m(2)/g.

Aluminosilicate relatives: Chalcogenoaluminogermanates Rb(3)(AlQ(2))(3)(GeQ(2))(7) (Q = S, Se).

The new compounds Rb(3)(AlQ(2))(3)(GeQ(2))(7) [Q = S (1), Se (2)] feature the 3D anionic open framework [(AlQ(2))(3)(GeQ(2))(7)](3-) in which aluminum and germanium share tetrahedral coordination sites. Rb ions are located in channels formed by the connection of 8, 10, and 16 (Ge/Al)S(4) tetrahedra. The isostructural sulfur and selenium derivatives crystallize in the space group P2(1)/c.

Novel P-Se anions and their copper complexes.

Three reactions of Cu(i) thiolates and Woollins' reagent (W.R.) give rise to novel copper complexes with unusual P/Se anions.

The anhydride route to Group 15/16 ligands in oligomeric and polymeric environments: from metal complexes to supraionic chemistry.

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.

A recipe for new organometallic polymers and oligomers? Synthesis and structure of an oligo- and a polymeric arrangement of P-S anions.

A route to organometallic polymers and oligomers is described using metal complexes with P/S-ligands as examples.

Polymeric organometallic architectures of novel P-Se anions.

The characterisation of a series of compounds obtained from Woollins' reagent (W.R.) offers a novel approach to organometallic coordination polymers.

Metal thiophosphonates and related compounds: an emerging area of supramolecular coordination chemistry.

Nine new compounds containing PS ligands of the types [P(OtBu)S3]2-, [ArP(StBu)S2]- and [ArP(OtBu)S2]- are reported (Ar = 4-anisyl). It is demonstrated that the topology of alkali metal ion and ligand composition influence the structure of supramolecular arrangements.

Polymeric arrangements of P-Se anions and a first insight into their reactivity.

The reactions of the P/Se-precursor Woollins' reagent [PhP(Se)mu-Se]2 with alkali-metal salts offer new perspectives for the synthesis of metal aggregates containing P-Se anions. Depending on the alkali-metal thiolates polymeric arrangements of [PhPSe3]2- or [PhPSe2Se-SeSe2PPh]2- dianions are observed and the mechanisms of their formation described.

Reactions of P/S-containing proligands with coinage metal salts: a new route to polynuclear complexes with unusual structural types.

The reactions of P/S-precursors with coinage metal alkoxides and carboxylates offer new perspectives for the synthesis of complex metal aggregates.

A strategy for the build-up of transition-metal complexes containing tripodal [ArPOS2]2- and [ArPS3]2- ligands (Ar = 4-anisyl).

The investigation presents new synthetic methods for the generation of tripodal P/S ligands by reactions of metal alkoxides and carboxylates with the organoperthiophosphinic acid anhydride Lawesson's reagent. Four new transition-metal complexes containing various tripodal ligand sets were synthesised and characterised.

Functionalised trimethylsilyl reagents in cluster synthesis: reactions of Ph2P(S)SSiMe3 with group 11 salts.

A series of complexes, ranging from the small cluster 1/infinity[Ag(Ph2PS2)(dppe)](infinity) [dppe=1,2-bis(diphenylphosphino)ethane] to [Cu48S20(O(t)Bu)2(Ph2PS2)2(dppm-)4(dppm)4][dppm=1,2-bis(diphenylphosphino)methane] (the largest Cu cluster containing phosphinodithioato ligands), has been synthesised. The structural evidence presented here indicates that in these reactions initially small cyclic aggregates or one-dimensional coordination polymers are formed. The growth of these intermediates to larger aggregates can take up to several months and could proceed via cationic intermediates.