Struttura cristallina della catena di μ \mu \ -(oftalato)cuprato(II) di dirubidio diidrato

The crystal structure of dirubidium catena-di- $\mu \$ (ophthalato)cuprate(II) dihydrate has been determined by an X-ray analysis. The structure was solved by Patterson and Fourier methods and refined by block-diagonal least-squares (final R = 6,6%). The structure consists of nearly planar-square complexes formed by four oxygen atoms belonging to four phthalate ions. Each phthalate ion bridges two copper atoms, so the coordination polyhedra are Joined together in chains parallel to [001]

Nucleophylic attack of amine and hidroxide to platinum-dichlorobenzonitrile. Crystal structure of [Pt(NH=CPhNButCH2CH2NHBut)Cl(NHCOPh)], 2, and cis [Pt(NH=CPhNButCH2CH2NHBut)Cl2(NCPh)], 3

The trans and cis isomers of [PtCl2(NCPh)2] react with N,N′-di-tert-butylethylenediamine (t-Bu2en) under normal conditions to give [Pt(NH=CPhN-t-BuCH2CH2NH-t-Bu)Cl(NCPh)]Cl (1) and cis-[Pt(NH=CPhN-t-BuCH2CH2NH-t-Bu)Cl2(NCPh)] (3), respectively. In both cases one end of t-Bu2en adds to benzonitrile forming an amino-amidine ligand which is chelated in 1 (forming a seven-membered metallacycle) and monocoordinated in 3. The residual benzonitrile in the cationic complex 1 readily reacts with base to give a benzamidate species, [Pt(NH=CPhN-t-BuCH2CH2NH-t-Bu)Cl-(NHCOPh)] (2). Compound 3 exhibits, in solution, isomerization about the azomethine double bond (Δ‡223 = 10.8 ± 0.3 kcal mol-1) and more slowly undergoes an internal rearrangement with substitution of the residual benzonitrile by the uncoordinate end of the diamine and formation of [Pt(NH=CPhN-t-BuCH2CH2NH-t-Bu)Cl2] (4). The structures of 2 and 3 have been solved by single-crystal diffraction. Compound 2 crystallizes as methanol solvate (1:1) in the monoclinic space group P21/n with a = 25.374 (13) Å, b = 11.351 (8) Å, c = 9.338 (5) Å, β = 92.03 (4)°, and Z = 4. Compound 3 crystallizes as toluene solvate (2:1) in the monoclinic space group P21/a with a = 18.090 (10) Å, b = 9.376 (4) Å, c = 17.297 (7) Å, β = 91.76 (4)°, and Z = 4. Both compounds contain a strong intramolecular hydrogen bond which involves the oxygen atom of the benzamidate anion and the cis amine group of the chelate amino-amidine ligand in 2, the free and coordinate ends of the monocoordinate amino-amidine ligand, so forming a pseudo-seven-membered ring, in

Pyrazolate bridged dinuclear rhodium complexes. X-ray structure of [Rh(Pz)(CO)P(OPh)3]2

The synthesis and properties of complexes of general formulae [Rh(Pz)(CO)L]2 (Pz = pyrazolate ion, L = phosphorus donor ligand), [Rh(Pz)(diolefin)]2 and [Rh(Pz)(C2H4)2]2 are reported. The crystal structure of the novel complex [Rh(Pz)(CO)P(OPh)3]2 has been determined by X-ray methods. The crystals are triclinic, space group P1, with Z = 2 in a unit cell of dimensions a 14.061(10), b 17.140(13), c 9.937(7) Å, α 102.19(7), β 10.9.55(8), γ 75.14(8)°. The structure has been solved by Patterson and Fourier methods and refined by full-matrix least-squares to R = 0.058 for 2514 independent observed reflections. The structure consists of discrete dimeric complexes in which each rhodium is in nearly square-planar arrangement, being bonded to a carbon atom of a carbonyl group, to a phosphorus of a triphenylphosphite ligand and to two nitrogen atoms of pyrazolate ligands bridging the metal atoms. The dihedral angle between the two square planes of 86.2° gives a bent configuration to the molecule in which the carbonyls and the phosphite ligands are in a trans arrangement.Peer reviewe

Tris(pentafluorophenyl) neutral and anionic five-co-ordinate complexes of rhodium(III). Crystal structures of [Rh(C6F5)3(PEt3)2] and [Rh(C6F5)3(AsPh3)2]

The binuclear compound [P(CH2Ph)Ph3]2[{Rh(µ-Cl)(C6F5)3}2](1) has been prepared by reaction of HCl with [P(CH2Ph)Ph3]2[Rh(C6F5)5](2) in methanol. Treatment of (1) with thallium(I) acetylacetonate has given the anionic complex [P(CH2Ph)Ph3][Rh(acac)(C6F5)3](acac = acetylacetonate). Addition of neutral ligands L to (1) yields anionic derivatives of the type [P(CH2Ph)Ph3][RhCl(C6F5)3L][L = pyrazole (Hpz), pyridine (py), PPh3, AsPh3, or CO](3)–(7) and the reaction of (1) with AgClO4 in the presence of 2 mol of neutral ligands gives rise to neutral compounds [Rh(C6F5)3L2][L = P(OMe)3, PPh3, PEt3, AsPh3, py, Hpz, 4-methylpyrazole, or 3,5-dimethylpyrazole](8)–(15). The crystal structures of the complexes [Rh(C6F5)3(PEt3)2](10) and [Rh(C6F5)3(AsPh3)2](11) have been determined by X-ray diffraction methods. Both structures consist of very flattened square-pyramidal complexes in which two C atoms from C6F5 groups and two P from PEt3 ligands [(10)], or two As from AsPh3 ligands [(11)], occupy the basal positions, whereas the third C atom from a C6F5 ligand lies at the apex.We thank the Direccion General de Investigacion Cientifica y Tecnica (Spain) (Projects PB 88-0386 and PB 87-0289) for financial support.Peer reviewe

A homoleptic mononuclear iridium(II) organometallic complex: synthesis and x-ray structure of [Ir(C6Cl5)4]2-

The homoleptic indium(II) diamomc complex [Ir(C6Cl5)4]2- has been prepared from [\Ir(p-Cl)((cyclooctene)^í] and Li(CgClg) in EtiO at -50 °C. It reacts with carbon monoxide affording the iridium(I) complex [Ir(CgClg)3(CO)]2~. Both, dianionic complexes have been fully characterized by elemental analyses, by MS, and by several physical properties. The crystal structure of [PBzPh3]2[Ir(C6Cl5)4]. CH2Cl2(1) has been established by an X-ray diffraction study. 1 crystallizes in the monoclinic space group C2/c with a =19.355(8) A, b = 18.188(6) A, c=22.691(9) A, ß=102.82(2)°, V =7789(5)A3, Z =4, µ= 25.53 cm'1 5, and dcak - 1.690 g-cm~3. Theanionic iridium(II) complex has an imposed Cisymmetrywith the 2-fold axis bisecting two pentachlorophenyl groups. The coordination around the Ir atom is almost perfectly square planar. The dispositions of the aryl rings with respect to the metal coordination plane are all inclined in the same way conforming a propeller-like shape for the iridium(II) complex.We thank the CICYT (Comisión Interministerial de Ciencia y Tecnología) (Project MAT93-1019-E) and the CSIC-CNR Joint Program for financial support.Peer reviewe