Ionel Haiduc

Metal compounds in cancer chemotherapy

Revue synthetique de complexes metalliques utilisables en chimiotherapeutique. Synthese bibliographique

Supramolecular Organometallic Chemistry

Basic Concepts and Principles. Molecular Recognition and Host-Guest Interactions. Supramolecular Self-Assembly by Dative Bonds (Electron-Pair Donor-Acceptor or Lewis Acid-Base Interactions). Supramolecular Self-Assembly by Formation of Secondary Bonds. Supramolecular Self-Assembly by Hydrogen-Bond Interactions. Supramolecular Self-Assembly Caused by Ionic Interactions. Supramolecular Self-Assembly as a Result of PI-Interactions. Subject Index.

Thiophosphorus and related ligands in coordination, organometallic and supramolecular chemistry. A personal account

Abstract The results obtained in the investigation of sulfur containing ligands (dithiophosphates, -phosphinates and -phosphonates, monothiophosphinates, dithioarsinates and dichalcogenoimidodiphosphinates) in a broad international cooperation, are concisely presented. Oxo- and thio-organophosphorus and -organoarsenic anions are versatile ligands in metal and organometallic derivatives, with molecular monomeric, cyclic or supramolecular structures, at the interface between the traditional branches of inorganic chemistry: coordination, organometallic and inorganic ring chemistry.

Structural patterns in inorganic and organoantimony derivatives of oxo- and thiodiorganophosphorus ligands

Abstract The structures of inorganic and organoantimony complexes of diorganophosphorus ligands and their thio analogues, determined by X-ray diffraction, are reviewed with particular attention given to the coordination geometry around the metal atom and the coordination pattern of the phosphorus ligands.

Tellurium⋯π-aryl interactions: a new bonding motif for supramolecular self-assembly and crystal engineering

A search of the Cambridge Structural Database (CSD) was performed to identify Te⋯π-aryl interactions not reported before in the literature. The examination of the distance between tellurium atoms and aryl group centroids and the analysis of crystal packing, using deposited crystal structure data, produced a list of organotellurium compounds which showed a variety of Te⋯π bonding interactions. These include inter-ionic Te⋯π interactions in anion–cation ion pairs, intramolecular Te⋯π-aryl interactions in mono- and di-nuclear covalent molecular compounds, as well as in dimeric and tetrameric supermolecules or in supramolecular polymeric arrays formed through secondary bonds. Most interesting was the finding that intermolecular Te⋯π aryl interactions can connect molecular tectons, leading to supramolecular self-assembly with formation of dimeric and polymeric superstructures. Finally, Te⋯π aryl interactions may interconnect polymeric chains formed through Te⋯X secondary bonds into 2D and perhaps 3D networks. Thus, the Te⋯aryl interactions appear as a new bonding motif for supramolecular self-assembly, which could be exploited for crystal engineering in organotellurium chemistry, i.e. for the design of new materials with attractive useful properties.

Supramolecular associations, secondary bonds, quasi-cyclic structures and heterogeometrism in metal derivatives of phosphorus- and arsenic-based thioacids and oxo analogs

Abstract The structural features of complexes involving thiophosphorus and thioarsenic ligands bound to transition metal and Main Group elements are described. Intermolecular associations are very common and are discussed in the context of supramolecular chemistry.

A new inorganic metallocycle containing tin, sulphur, phosphorus and nitrogen. Crystal and molecular structure of spirobicyclic Me2Sn(SPPh2NPPh2S)2

Abstract A new inorganic heterocycle is obtained by reacting potassium tetraphenyldithioimidodiphosphinate with trimethyltin and dimethyltin chlorides, in benzene. X-ray diffraction analysis reveals a spirocyclic structure with the dimethyltin moiety as the coordination centre with non-planar six-membered SnS 2 P 2 N rings. The coordination at tin is nearly perfectly octahedral, with equal SnS [273.3(2) and 273.7(2) pm] and PS bonds [200.9(3) and 201.9(3) pm]. The SSnS and H 3 CSnCH 3 units are co-linear.

Antimony(III) diorganophosphoro- and diorganophospinodithioates: Crystal structure of Sb[S2P(OR)2]3 (R = Me and i-Pr)

Abstract Several antimony(III) tris(dialkylphosphorodithioates) Sb[S 2 P(OR) 2 ] 3 (R = Me, Et, i-Pr, n-Bu, i-Bu and sec-Bu) and tris(diorganophosphinodithioates Sb(S 2 PR 2 ) 3 (R = Me, Et and Ph) have been prepared by reactions between antimony trichloride and respectively the ammonium and sodium salts of the corresponding acid. The compounds were characterised by infrared and 1 H NMR spectroscopy and the structures of two phosphorodithioates (R = Me and i-Pr) have been determined by X-ray diffraction. Each antimony atom is surrounded by six sulphur atoms from three anisobidentate phosphorodithioate ligands with three atoms at 2.528 and three at 3.010 A. The overall arrangement is distorted octahedral and although this geometry is consistent with stereochemical activity of the 5s electrons at antimony, it cannot be interpreted as direct proof.

Phenylantimony(III) diorganophosphorodithioates: the crystal structure of diphenylantimony(III) di-isopropylphosphorodithioate, Ph2SbS2P(OiPr)2; unusual polymerisation through semibonding

Abstract The diphenylantimony(III)phosphorodithioates, Ph 2 SbS 2 P(OR) 2 where R = Me, Et, i Pr and Ph, have been prepared and the methyl and isopropyl derivatives obtained as crystalline solids. The compounds have been characterised by infrared and NMR spectroscopy. An X-ray structural determination for the isopropyl compound shows the presence of two independent molecules in the asymmetric unit, with similar but not identical molecular parameters. The ligand in each molecule is strongly bonded to antimony by one sulphur atom (SbS 2.54 A), but there are two weaker SbS contacts ( ca. 3.2 and 3.8 A) making the ligand effectively tridentate. These interactions generate infinite chains in the solid state, providing an example of a new dithiophosphate structure.

Tetrahedral versus square-planar NiS4 core in solid-state bis(dithioimidodiphosphinato)nickel(II) chelates. Crystal and molecular structures of Ni[(SPR2) (SPPh2) N]2 (R = Ph, Me)

Abstract Bis(dithioimidodiphosphinato)nickel(II) chelates, Ni[(SPR2) (SPPh2)N]2 (R = Ph (1), Me (2)) were prepared by methathesis reactions between NiCl2·6H2O and the corresponding potassium dithioimidodiphosphinate, in methanol. Compound 1 crystallizes in the triclinic space group P-1, a = 13.336(2), b = 18.580(2), c = 18.670(2) A , α = 90.10(2), β = 93.00(2), γ = 98.21(2)°, Z = 4 , and contains two independent molecules in the unit cell. Compound 2 crystallizes in the monoclinic space group P2 1 /c, a = 13.161(2), b = 10.737(5), c = 12.101(4) A , β = 108.38(2)°, Z = 2 . In both compounds the 1,3-dithiophosphorus ligands act as symmetrical monometallic biconnective (isobidentate chelating) units and the resulting NiS2P2N rings are non-planar. Compound 1 contains a tetrahedral NiS4 core (mean NiS 2.239 A, SNiS 111.9° (endocyclic), 108.2° (exocyclic)), while compound 2 exhibits a square-planar NiS4 core (mean NiS 2.239 A, SNiS 98.3° (endocyclic), 81.1° (exocyclic)). The structures are discussed in relation to previously reported Ni(II) derivatives of 1,1-dithiophosphorus ligands.