Patricia y García

THE PREPARATION AND X-RAY STRUCTURE OF M(SEPPH2)2N)2, M = NI, PD, PT

Abstract Reaction of [Ni(CH3CO)2]4H2O, H2PdCl4 or H2PtCl6 with HN[P(Se)Ph2]2 in water/acetone gave the title compounds in good yield. The compounds were characterised by IR/Raman, NMR and X-ray crystallography. The square planar metal centres form parts of spiro pseudo-boat rings. The X-ray structures allow comparison of the radii of Pt and Pd atoms.

A true square-planar tin(II) spiro complex: molecular structure of bis(imidotetraphenyldiselenodiphosphino-Se,Se′)tin(II) and its distorted tetragonal-pyramidal isomer

The yellow complex [Sn{N(SePPh2)2-Se,Se′}2] is the first example of a true square-planar spiro tin(II) compound; the structure of the distorted tetragonal-pyramidal isomer is also described.

Synthesis, characterization and X-ray structure of stannocanes substituted with a cyclic dithiophosphate ligand X(CH2CH2S)2SnnBu [S2P(OCH2C(Et2)CH2O)], (X=O, S): a study about the conformational tendencies and the relationship with the anomeric effect of the stannocane rings

Abstract The preparation and conformational study of two stannocanes, 5-n-butyl-5-(5′,5′-diethyl-2′-thioxo-1′,3′,2′-dioxaphosphorinane-2′-thiolate)-1-oxa-4,6-dithia-5-stannocane, O(CH2CH2S)2SnnBu[S2P(OCH2CEt2CH2O)] (1) and 2-n-butyl-5-(5′5′-diethyl-2′-thioxo-1′,3′,2′-dioxaphosphorinane-2-thiolate)-1,3,6-trithia-2-stannocane S(CH2CH2S)2SnnBu[S2P(OCH2CEt2CH2O)] (2) is reported. These compounds were prepared from the corresponding chloro-oxa and -thia-stannocanes and the sodium salt of dithiophosphoric acid (2-mercapto-2-thiono-1,3,2-dioxaphosphorinane) in ethanol. Compounds 1 and 2 were characterized by IR, EI-MS and multinuclear NMR (1H, 13C, 31P). The molecular structures were determined by X-ray analyses. The eight-membered ring in both compounds has a boat–chair conformation with a 1,5 transannular Sn⋯O (2.468 A), Sn⋯S (2.94 A) interaction. The 1,3,2-dioxaphosphorinane ring in 1 and 2 present a chair conformation with the stannocane in the axial position, in accordance with the anomeric effect. The coordination of the Sn-atoms is trigonal-bipyramidal in 1 and intermediate between trigonal-bipyramidal and a bicapped tetrahedral arrangement in 2.

Influence of the steric effect on the conformation of stannocanes. The synthesis and X-ray structure of X(CH2CH2S)2Sn(n-Bu)Cl (X=S, O)

Abstract 5-Chloro-5- n -butyl-1-oxa-4,6-dithia-5-stannocane ( 1 ) and 2-chloro-2- n -butyl-1,3,6-trithia-2-stannocane ( 2 ) have been prepared by reacting n -butyltin trichloride with 2-mercaptoethyl ether and 2-mercaptoethyl sulphide, respectively. Complexes 1 and 2 were characterised by elemental analyses, IR, EI MS, and multinuclear NMR ( 1 H, 13 C, 119 Sn). The molecular structures of 1 and 2 were determined by X-ray analyses. The eight-membered rings in both compounds are in the boat–chair conformation with a 1,5 transannular Sn⋯O (2.409(7) A) or Sn⋯S (2.7855(16) A) interaction. The coordination around the Sn atoms can be described as trigonal bipyramidal with Cl and X in the apical positions.

1-Oxa-4,6-Dithia-5-Arsocane and 1,3,6-Trithia-2-Arsocane Dithiocarbamates Competition Between Transannular and Exocyclic Secondary Bonding to Arsenic

1-oxa-4,6-dithia-5-arsocane morpholinyldithiocarbamate (1) and 1,3,6-trithia-2-arsocane 2-diethyldithiocarbamate (2) have been prepared by reacting the corresponding sodium dithiocarbamates with 1-oxa-4,6-dithia-5-arsocane or 1,3,6-trithia-2-arsocane. (1) and (2) were characterized by elemental analyses, IR, MS, 1H and 13CNMR. The X-ray single-crystal molecular structures of (1) [monoclinic, a = 9.931(5), b = 18.253(5), c = 8.076(3) A; β = 92.56(2)°; V = 1462.5(7) A3; space group P21/c; Z = 4; R = 4.33%] and (2) [monoclinic, a = 7.830(2), b = 10.465(2), c = 19.025(6) A; β = 95.82(2)°; V = 1550.8(10) A3; space group P21/c; Z = 4; R = 3.41%], show that the compounds are monomeric and contain an asymetric monometallic biconnective dithiocarbamate ligand with a large distortion in the geometry around the As and a weak heterocyclic arsocane transannular secondary interaction.

Coordination ability of the heterocycles 1,3-dithia-2-arsa- and -stiba-cyclopentanes towards sulfur containing ligands, part II. Diheterocyclic dithiocarbamate complexes. X-ray structure of the 4-morpholinecarbodithioate of 1,3-dithia-2-arsa-cyclopentane

SummaryA series of diheterocyclic dithiocarbamate complexes of the typeRNCS2MS2C2H4, whereR=pyrrolidyl, 3-pyrrolyl, 4-morpholyl, 3-methlpiperidyl andM=As or Sb were obtained and characterized by IR,1H, and13C-NMR, mass spectroscopy and elemental analyses. The X-ray crystal structure determination of the 4-morpholinecarbodithioate of 1,3-dithia-2-arsa-cyclopentane shows a monodentate behaviour of theRNCS2 entity.ZusammenfassungEs wurden eine Reihe von diheterocyclischen Dithiocarbamat-Komplexen des TypsRNCS2MS2C2H4 mitR=Pyrrolidyl, 3-Pyrrolyl, 4-Morpholyl, 3-Methylpiperidyl undM=As oder Sb hergestellt und mittels IR,1H- und13C-NMR, MS und Elementaranalysen charakterisiert. Die Röntgenstrukturanalyse des 4-Morpholinocarbodithioats von 1,3-Dithia-2-arsa-cyclopentan zeigt ein monodentates Verhalten derRNCS2-Einheit.

On the easy oxidation of (R)-2-[N-(1-phenylethyl)amino]-1-cyclopentenedithiocarboxylic acid to its disulfide dimer

Abstract The physical and spectroscopic data of (R)-2-[N-(1-phenylethyl)amino]-1-cyclopentenedithiocarboxylic acid are reviewed and the synthesis of (R)-di-[2-(N-(1-phenylethyl)amino]-1-cyclopentenedithiocarboxylic acid disulfide is described. The product resulting from the conjugate addition of the dithioacid to 2(5H)-furanone is also characterised.

Structural diversity of four-co-ordinate metal(II) compounds with the bidentate bis(diphenylselenophosphoryl)amide ligand, [M{N(PPh(2)Se)(2)-Se,Se'}(2)] (M=Sn, Pb, Zn, Cd or Hg)

The [N(PPh 2 Se) 2 ] - ion formed stable bis-chelates with M II (M = Sn, Pb, Zn, Cd or Hg), [M{N(PPh 2 Se) 2 -Se,Se′ } 2 ], which exhibit a large diversity of structural arrangements around the metal, as shown by X-ray crystallography. The tin(II) complex crystallises dimorphically, as yellow triclinic prisms (1) and red tetragonal octahedrons (1′). The yellow isomer is square planar, representing the first example of a true square-planar tin(II) spiro-compound. The red isomer and the lead(II) compound (2) exhibit a distorted ψ-trigonal-bipyramidal co-ordination geometry with a vacant equatorial position, which suggests the presence of a stereoactive electron lone pair. The cadmium(II) and mercury(II) complexes (3 and 4) are tetrahedral.

Organometallic tin(IV) derivatives of the ambidentate O-cholesteryl-O-phenyl phosphorothioate ligand

Abstract Organotin(IV) compounds of the potentially ambidentate O-cholesteryl-O-phenyl phosphorothioate ligand formulated as Me3SnOSPR′R′′ (1), Ph3SnOSPR′R′′ (2), O(CH2CH2S)2Sn(n-Bu)OSPR′R′′ (3), S(CH2CH2S)2Sn(n-Bu)OSPR′R′′ (4), (R′=O-Ph; R′′=O-cholesteryl) were obtained and characterized by elemental analyses, IR, MS and multinuclear NMR (1H, 13C, 31P and 119Sn) spectroscopy. The spectroscopic data are consistent with bonding of the phosphorothioate ligand through both sulfur and oxygen atoms to the Sn(IV) center.

Synthesis and characterization of the new ambidentate O-cholesteryl-O-phenyl phosphorothioate ligand and its organoarsenic derivatives of phenoxarsin-10-yl and phenothiarsin-10-yl phosphorothioate

A new anionic phosphorothioate ligand that incorporates the bioactive cholesteryl group was obtained (2), Na(RR′P(S)O; R, O-phenyl; R′, O-cholesteryl) from the phenylphosphoramidate (1) and NaH in dioxane. In order to test the coordination ability of 2, two organoarsenic derivatives were prepared, O(C6H4)2AsS(O)PRR′ (3) and S(C6H4)2AsS(O)PRR′ (4) by reacting 2 with 10-chlorophenoxarsine or 10-chlorophenothiarsine. Compounds 2, 3, and 4 were characterized by elemental microanalysis, IR, multi-element NMR (1H, 13C, and 31P), and mass spectrometry. The spectroscopic data suggest that the ligand is bonded to the arsenic only through the sulfur donor atom in both organoarsenic derivatives.