http://users.auth.gr/akrivos/Metaptyxiaka/Proxorimeni%20Anorgani/Coord_Chem_Rev_145_1995_157.pdf

The molecular structure of organogermanium compounds

Cyclic and Heterocyclic Thiazenes

Publisher Summary This chapter attempts to cover several kinds of heterocycles containing the sulfamide moiety. Earlier reports dealt with cyclic sulfamides, and with the chemistry of thiadiazole and thiadiazine S-oxides. These compounds have also been mentioned in Comprehensive Heterocyclic Chemistry. There has been extensive work on the chemistry and reactions of sulfamide and of alkylsulfamoyl chlorides that include heterocycles of this kind. This chapter offers a more extensive scope, since it covers some aspects of thiadiazines and thiadiazoles, such as tautomerism and aromaticity that had not previously been dealt with. It also includes other heterocycles. This article has been divided on the basis of the nature and size of the heterocyclic ring. The size of the rings range from three- to nine-membered heterocycles, although a ring with 30 members has also been described. A variety of biological activities are reported for different heterocycles containing the sulfamide moiety. For the sake of brevity, they are listed together with their respective structures.

Heterocycles containing the sulfamide moiety

Palladium and Platinum

The treatment of cis-[PtII(L1a/b-S,O)2] complexes of N,N-diethyl- (HL1a) and N,N-di(n-butyl)-N’-benzoylthiourea (HL1b) with I2 or Br2 in chloroform, leads to rapid oxidative addition to yield several geometric isomers of [PtIV(L-S,O)2X2]
				(X = I, Br); the reactions can be monitored by 195Pt NMR and UV-visible spectrophotometry. The products cis-[PtIV(L1a-S,O)2I2]
				6 and cis-[PtIV(L1a-S,O)2Br2]
				7, which have been isolated and structurally characterized, are the first-reported crystal structures of complexes of Pt(IV) with this class of ligand. Molecules of 6 pack such that the I–Pt–I axes are essentially aligned, with unusually close nearest-neighbour iodide contacts (3.553(1)
				A). These short I⋯I intermolecular interactions lead to infinite chains of weakly connected molecules in crystals of the compound. No such interactions are evident in the corresponding crystals of 7. Reaction of the Pt(II) complex of N-propyl-N’-benzoylthiourea (H2L2a)
				cis-/trans-[PtII(H2L2a-S)2Br2] with Br2 also results in oxidative addition, to yield trans-PtIV(H2L2a-S)2Br49. By contrast, treatment of cis-/trans-[PtII(H2L2a-S)2I2] with I2 does not lead to an oxidative addition product, yielding instead an interesting iodine inclusion compound of PtII, trans-[PtII(H2L2a-S)2I2]·I28. In 8, short intermolecular I⋯I distances of 3.453(1)
				A between I2 and coordinated iodide ions in trans-[PtII(H2L2a-S)2I2] molecules, result in infinite chains of weakly linked trans-[PtII(H2L2a-S)2I2]⋯I2 groups in the lattice. However, the empirically estimated bond order of 0.75 for the included I2 molecules does not support the possible existence of discrete tetraiodide ions (I42−) in the lattice of compound 8.

/pdf/reactions-of-halogens-with-pt-ii-complexes-of-n-alkyl-and-n-1kf4lxbozs.pdf

Reactions of halogens with Pt(II) complexes of N-alkyl- and N,N-dialkyl-N′-benzoylthioureas: Oxidative addition and formation of an I2 inclusion compound

Die Umsetzung von S4N4O2 mit Nucleophilen (Alkoholate, Alkohole, Azide und Isocyanate) in alkoholischem Medium fuhrt zu den Salzen 1a–h. Fur 1h wurde eine Rontgenstrukturanalyse durchgefuhrt. 1h kristallisiert in der Raumgruppe P21/n und enthalt eine transannulare SS Bindung mit 248.2 (2) pm. Die Struktur von 1h wird im Zusammenhang mit der Zunahme der Elektronendichte betrachtet und mit den Ergebnissen der Rontgenstrukturanalyse von CH3Si(NSN)3SiCH3 (2) verglichen. 2 kristallisiert kubisch (Raumgruppe P4132). Das bicyclische Molekul (SN 150.4 (2), SiN 173.7 (2)pm) hat praktisch D3h Symmetrie und zeigt keine SS-Bindungen im Ring.



Salts of S4N4O2 – Examples for the Dependence of the Structure of Cyclic Sulfur-Nitrogen Compounds on the Electron Density



The reaction of S4N4O2 with nucleophiles (alcoholates, alcohols, azides, and isocyanates) in alcoholic solution leads to the salts 1a–h. The Structure of 1h was determined by means of an X-ray analysis. 1h crystallizes in the space group P21/n and contains a transannular SS-bond with 248.2 (2) pm. The structure of 1h is considered in connection with the increase of electron density and compared with the results of the X-ray analysis of CH3Si(NSN)3SiCH3 (2). 2 is cubic (space group P4132). The bicyclic molecule (SN 150.4(2), SiN 173.7 (2) pm) has approximate D3h symmetry and shows no SS bonds across the rings.

Hans-Jürgen Korte

Papers

Salze des S4N4O2 – Beispiele für die Abhängigkeit de Struktur von cyclischen Schwefel‐Stickstoff‐Verbindungen von der Elektronendichte

Tetrakis(imidazole)platinum(ii) bis(triiodides). the crystal and molecular structure of tetrakis(1,2‐dimethylimidazole)platinum(ii) bis(triiodide)

Kristall-und molekülstrukturen zweier modifikationen de hexaphenyldigermylsulfids (C6H5)3GeSGe(C6H5)3