{2,6-Bis[(pyridin-2-yl)sulfanylmeth-yl]pyridine-κ(2) N,N'}(η(3)-prop-2-en-yl)palladium(II) hexa-fluoro-phosphate.

The title compound, [Pd(C3H5)(C17H15N3S2)]PF6, is built up by a [(η(3)-all-yl)Pd](2+) fragment coordinated by a 2,6-bis-[(pyridin-2-yl)sulfanylmeth-yl]pyridine ligand coordinated through the N atoms. One of the S atoms is at a close distance to the metal centeratom [3.2930 (8) Å]. The Pd(II) atom is tetra-coordinated in a strongly distorted square-planar environment mainly determined by the η(3)-allyl anion in which the central C atom is disordered over two equally occupied positions. The crystal packing is very compact and is characterized by a three-dimensional network of C-H⋯F interactions between the F atoms of each anion and several H atoms of the surrounding cationic complexes.

Dithioether ligands containing a 2,6-disubstituted pyridine linker with two thioether-heterocycle arms.

The structure of 2,6-bis(2-pyridyltsulfanylmethyl)pyridine (pytmp), (I), C(17)H(15)N(3)S(2), presents a twisted conformation, with the three planar moieties almost perpendicular to each other. The structures of two related derivatives, namely 2,6-bis(6-methyl-2-pyridylsulfanylmethyl)pyridine (mpytmp), (II), C(19)H(19)N(3)S(2), and 2,6-bis(4-methyl-2-pyrimidylsulfanylmethyl)pyridine (mprtmp) n-pentane hemisolvate, (III), C(17)H(17)N(5)S(2).0.5C(5)H(12), present extended planar fragments with just one quasi-perpendicular arylsulfanylmethyl side arm, such that the molecules are folded in an L-shaped conformation. All three conformations appear different from those adopted by similar compounds, demonstrating the great flexibility of such species, although such differences in conformational behaviour might drive specific coordination modes.

195Pt NMR of heteropolymetallic complexes containing secondary dithiooxamides as binucleating ligands.

Monometallic [Pt{S-S2C2(NR)2H}2] (S-S2C2(NR)2H = kappa2-S,S-S2C2(NR)2H = bis-dialkyl-dithioxamidate, R = methyl, isoamyl, benzyl) and binuclear and trinuclear heterobimetallic complexes [Pt{S-S2C2(NR)2H}{mu-S2C2(NR)2}MLn] (mu-S2C2(NR)2 = kappa2-S,S(Pt)-kappa2-N,N(M)-S2C2(NR)2) and [Pt{{mu-S2C2(NR)2}MLn}2] (MLn+ = [(eta3-allyl)palladium]+, [bis-(2-phenylpyridine)rhodium]+, [(eta6-p-cymene)(chloro)ruthenium]+, [(1,4-cyclooctadiene)rhodium]+, [(pentamethylcyclopentadienyl)(chloro)rhodium]+) have been prepared and characterized. The progressive substitution of the residual amidic hydrogen in the [Pt{S-S2C2(NR)2H}2] complexes with a MLn+ metal fragment results in the deshielding of platinum nuclei, a red shift of the MLCT absorption maximum, and a decrease in the oxidation potential. Such behavior has been interpreted as a progressive electron shift from platinum to the binucleating ligands, the extent of which depends on the nature of MLn+ metal fragment.

Redox-active dirhodium(II,II) species covalently entrapped into a methylmethacrylate backbone.

A novel class of polymers was obtained by insertion of dirhodium(II,II) metal systems into a methacrylate backbone; the synthesis was realized by free radical polymerization of an appropriate methacrylate-functionalized dirhodium polymer precursor, namely [Rh2(form)2(MA-COO)2](form =N,N'-di-p-tolylformamidinate)(MA-COO = 2-(methacroyloxy)ethyl-phthalate), with methylmethacrylate (MMA); the new copolymers, in solution, show reversible CO-absorption, connected to the axial reactivity of dirhodium(II,II) species.

Bis(di-2-pyridyl sulfide-kappa2N,N')(4-methylpyrimidin-2-yl 2-pyridylmethyl sulfide-kappa2N,S)ruthenium(II) bis(hexafluorophosphate) acetonitrile solvate.

The crystal structure of the title compound, [Ru(C10H8N2S)2(C11H11N3S)](PF6)2.C2H3N, is composed of a bivalent octahedral RuII complex, two PF6- anions and an acetonitrile solvent molecule. Two PF6- units are found on a crystallographic binary axis, therefore contributing just one half each to the asymmetric unit cell. The structure displays a peculiar stereochemistry of the cation. Three bidentate ligands around the Ru centre, together with the coordination of the non-symmetric S atom, mean that these two atoms are chiral. This would lead to four stereoisomers, but only an enantiomeric pair was found in the analyzed sample.

Trinuclear heterobimetallic complexes with binucleating dithioxamides: stereoselective synthesis and solution behavior involving Pd-N bond rupture.

Bischelate platinum(II) complexes of the type [Pt(H-R(2)-N(2)C(2)S(2))(2)] (H-R(2)-N(2)C(2)S(2)(-) = dialkyl-dithioxamidate) are ditopic receptors which, after coordination of the first Pd(eta(3)-allyl)(+) moiety, induce the orientation of the second palladium-allyl fragment. Thus, a series of trimetallic complexes of formula bis-[(eta(3)-allyl)-palladium(II)](mu-bis-dialkyl-dithioxamidate-platinum(II) kappa-S,S-kappa-S',S'-Pt-kappa-N,N-Pd-kappa-N',N'-Pd') has been prepared in which the allyl fragments are oriented toward the same side of the molecular plane. We have also prepared the trimetallic complex using a dithioxamide obtained from the racemic phenylethylamine. Only two isomers were produced in equimolar ratio: the racemate that has four homochiral alkyl substituents and the mesoform containing the meso-dithioxamide that has homochiral substituents on the same side of molecular plane. Under the effect of the temperature, the trimetallic Pd-Pt-Pd complexes undergo rapid allyl isomerization; the mechanism of the isomerization, which is similar to that found by us in an analogue Pt-Pd bimetallic complex, is discussed. The crystal and molecular structure of bis-[(eta(3)-allyl)-palladium(II)](mu-bis-[S]-phenylethyl-dithioxamidate-platinum(II) kappa-S,S-kappa-S',S'-Pt-kappa-N,N-Pd-kappa-N',N'-Pd') has been reported.

N,N'-dibenzyldithiooxamide.

The title compound, alternatively known as N,N'-dibenzylethanedithioamide, C(16)H(16)N(2)S(2), lies about an inversion centre and contains a planar trans-dithiooxamide fragment characterized by a strong intramolecular hydrogen bond between the S atom and the adjacent amide H atom in the solid state, with an S...N distance of 2.926 (1) A. The aryl substituent is oriented orthogonal to the mean plane of the trans-dithiooxamide fragment due to steric hindrance and this effect is discussed.

(eta3-Allyl-2kappa3C)(chloro-1kappaCl)(micro-N,N'-diethyldithioxamidato-1:2kappa4S,S':N,N')[diphenyl(2-pyridyl)phosphine-1kappaP]palladium(II)platinum(II) chloroform solvate.

The title compound, [PdPtCl(C(3)H(5))(C(6)H(10)N(2)S(2))(C(17)H(14)NP)].CHCl(3), was obtained by deprotonation of the initial platinum(II) complex of the dithioxamide and subsequent reaction with [Pd(eta(3)-C(3)H(5))(micro-Cl)](2). Both metal atoms exhibit a square-planar coordination geometry, with the two planes forming a dihedral angle of 21.7 (2) degrees. The dithioxamide bis-chelating bridge is flat.

trans-diacetonitrilebis(di-2-pyridyl sulfide-N,N')ruthenium(II) bis(tetrafluoroborate) monohydrate.

The title complex, [Ru(C10H8N2S)2(CH3CN)2](BF4)2*H2O, is the product of the solvolysis of [Ru(dps-N,N)2(dps-N,S)](PF(6))2 (dps is di-2-pyridyl sulfide) in the presence of HBF4 in acetone-acetonitrile at room temperature. There are two independent cations, with the Ru atoms on inversion centres; each Ru atom has an octahedral geometry with the dps molecules behaving as N,N'-bidentate ligands and assuming a trans arrangement.