Rainer Vollmerhaus

S,S-Diorgano Derivatives of the P2N4S2 Ring

Abstract The reaction of [Li(Ph4P2N4S2R)THF]2 with alkyl iodides R′I produces the msymmetrically substituted derivatives Ph4P2N4(SR)(SR′) as lithium iodide adducts. The coordinated LiI is readily removed in CH3CN or CH2Cl2 to give the eight-membered rings in a boat conformation (∂ 31P = 14–17 ppm). The boat conformers readily isomerize to the corresponding chair somers (∂ 31P = 25–29 ppm) upon gentle heating.

New Macrocyclic Ligands with P2N4S2 Rings in the Framework

Abstract Several new macromolecules containing two Ph4P2N4S2 rings linked by meta-xylyl groups have been prepared.

Solid state and solution structures of dimeric organolithium derivatives of a P2N4S2 ring

An X-ray structural determination of the dimer [Li(Ph4P2N4Ph)·THF]2(THF = tetrahydrofuran) reveals a step-shaped structure; 7Li and 31P NMR investigations of [Li(Ph4P2N4S2R)·THF]2(R = Me, But, Ph), as a function of temperature and concentration, in THF solution show that this dimer is fluxional and indicate the presence of a second dimeric species.

Preparation and X-ray structure of [(Ph3P)2N][Se5C(Se)COMe]: an anionic derivative of the Se5C ring

The reaction of Potassium carbonate with red selenium in acetone, in the presence of [PPN]Cl[PPN =(Ph3P)2N], at 23°C produces [PPN][Se5C(Se)COMe] in which the anion is shown by X-ray crystallography to consist of a six-membered Se5C ring in a chair conformation with significant endocyclic–exocyclic Se–Se interactions.