Preparation and crystal structure of binuclear chloro{6-[[chloro(triphenylphosphine)platinum](mesitylimino)methyl]pyridin-2-yl}bis(triphenylphosphine)platinum(II)

Treatment of N,N′-bis(mesityl)pyridine-2,6-carboxyimidoyl dichloride, 1, in toluene solution with [Pt(PPh₃)₄] at 100 °C afforded a novel platinacyclic compound, 3, in 63% yield, instead of the expected compound 2. The molecular and crystal structures of the title compound, 3, have been determined by the single crystal X-ray diffraction technique. The coordination geometries around the Pt atoms are distorted square-planar. In the crystal structure, the molecules are linked by a pair of C–H···N hydrogen bonds into a centrosymmetric dimer with an ring, centred at (1/2,1/2,1/2).     

cis‐Dichloro(dimethyl sulfoxide‐S)(2‐methoxypyridine‐N)platinum(II)

The title complex, [PtCl₂(C₆H₇NO)(C₂H₆OS)], exhibits square‐planar geometry. The plane of the pyridine ring makes a dihedral angle of 67.2 (3)° with the square plane of the metal center. The S—O bond is nearly aligned with the adjacent Pt—N bond, leaving the methyl groups of the di­methyl sulfoxide ligand to stagger the Pt—Cl bond.     

cis‐Bis(3,6‐di­hydro‐2H‐1,2‐oxazine‐N)­di­iodo­platinum(II) and cis‐bis(3,4,5,6‐tetra­hydro‐2H‐1,2‐oxazine‐N)­di­iodo­platinum(II)

The title complexes, [Pt(C₄H₇NO)₂I₂], (I), and [Pt(C₄H₉NO)₂I₂], (II), possess similar square‐planar coordination geometries with modest distortions from ideality. For (I), the cis‐L—Pt—L angles are in the range 87.0 (4)–94.2 (3)°, while the trans angles are 174.4 (3) and 176.4 (3)°. For (II), cis‐L—Pt—L are 86.1 (8)–94.2 (6)° and trans‐L—Pt—L are 174.4 (6) and 177.4 (5)°. One 3,6‐di­hydro‐2H‐1,2‐oxazine ligand in (I) is rotated so that the N—O bond is out of the square plane by approximately 70°, while the N—C bond is only ca 20° out of the plane. The other oxazine ligand is rotated so that the N—C bond is about 80° out of the plane, while the N—O bond is out of the plane by approximately 24°. In (II), the 3,4,5,6‐tetra­hydro‐2H‐1,2‐oxazine ligands are also positioned with one having the N—O bond further out of the plane and the other having the N—C bond positioned in that fashion. Both ligands, however, are rotated approximately 90° compared with their positions in (I). In both complexes, this results in an unsymmetrical distortion of the I—Pt—N bond angles in which one is expanded and the other contracted. These features are compared to those of reported cis‐di­amine­di­iodo­platinum(II) complexes.     

trans‐Chlorido(phenyl)bis(triphenylphosphine)nickel(II) and its 1:1 cocrystal with chloridobis(triphenylphosphine)nickel(I)

Two conformational polymorphs of trans‐chlorido(phenyl)bis(triphenylphosphine)nickel(II), [Ni(C₆H₅)Cl(C₁₈H₁₅P)₂], (1), viz. orange needle‐shaped crystals (form I) and brown prism‐shaped crystals (form II), were obtained under different crystallization conditions from a mixture of toluene and n‐hexane, and characterized by single‐crystal X‐ray diffraction at low temperature. These two forms were compared with that published previously [Zeller, Herdtweck & Strassner (2003). Eur. J. Inorg. Chem. pp. 1802–1806], characterized at room temperature. Additionally, blue–green prisms of a 1:1 cocrystal of complex (1) with chloridobis(triphenylphosphine)nickel(I), (2), viz.trans‐chlorido(phenyl)bis(triphenylphosphine)nickel(II)–chloridobis(triphenylphosphine)nickel(I) (1/1), [Ni(C₆H₅)Cl(C₁₈H₁₅P)₂]·[NiCl(C₁₈H₁₅P)₂], (3), were obtained concomitantly with form I. In forms I and II, as well as in the cocrystal, the overall crystal packings are determined by an energetic interplay between intramolecular torsions and weak intermolecular C—H...π and C—H...Cl interactions.     

cis‐Di­phenyl­bis(1,3,5‐tri­aza‐7‐phospha­adamantane‐κP)platinum(II)

The structure of the title compound, [Pt(C₆H₅)₂(C₆H₁₂N₃P)₂] or [Pt(Ph)₂(PTA)₂] (where Ph is phenyl and PTA is 1,3,5‐tri­aza‐7‐phosphaadamantane), is discussed. Selected geom­etric parameters are: Pt—P = 2.2888 (16) and 2.2944 (17) Å, Pt—C = 2.052 (5) and 2.064 (6) Å, C—Pt—C = 84.6 (2)° and P—Pt—P = 99.28 (6)°. The effective cone angle for the PTA ligands was calculated as 113°.     

cis‐Bis(acetato‐κO)bis(dimethyl sulfide‐κS)platinum(II)

The title compound, cis‐[Pt(CH₃COO)₂(C₂H₆S)₂], crystallizes in the P2₁/c space group with a pseudo‐square‐planar coordination geometry. The complex forms centrosymmetric dimeric packing units, with C—H...O—Pt interactions and a short Pt...Pt distance [3.5868 (2) Å]. The coordination mode of the acetate ligands is monodentate and they are oriented almost perpendicular to the coordination plane. Cambridge Structural Database [Allen (2002). Acta Cryst. B 58 , 380–388] data show a preferred staggered conformation with respect to the coordination plane for Me₂S in complexes with Pt^II.     

Sorption recovery of platinum(II) and platinum(IV) chloro complexes with a heterochain sulfur-containing sorbent

The recovery of platinum(II) and platinum(IV) chloro complexes from hydrochloric acid and chloride solutions with a new heterochain S,N-containing sorbent, MITKhAT, was studied. The suggested mechanism of formation of platinum(II) mercapto-thio ether complexes in the course of sorption was confirmed by DFT calculations. The results of group and selective recovery of platinum metals with MITKhAT sorbent from simulated and real industrial solutions are reported.     

catena‐Poly[[bis(cis‐1‐tert‐butyltetrazole‐κN4)copper(II)]‐di‐μ‐chloro]

The title polymeric compound, [CuCl₂(C₅H₁₀N₄)₂]_n, is the first structurally characterized complex with a bulky 1‐alkyl­tetrazole ligand. The coordination polyhedron of the Cu atom is an elongated octahedron. The equatorial positions of the octahedron are occupied by the two Cl atoms, with Cu—Cl distances of 2.2920 (8) and 2.2796 (9) Å, and by the two N‐4 atoms of the tetrazole ligands, with Cu—N distances of 2.023 (2) and 2.039 (2) Å. Two symmetry‐related Cl atoms occupy the axial positions, at distances of 2.8244 (8) and 3.0174 (8) Å from the Cu atom. The [CuCl₂(C₅H₁₀N₄)₂] units form infinite chains extended along the b axis, linked together only by van der Waals interactions. The skeleton of each chain consists of Cu and Cl atoms.     

Nitrato(triphenylphosphine) complexes of the platinum metals; Detection of triphenylphosphine oxide ligands

Reactions of some platinum group metal triphenylphosphine complexes with nitric acid afford nitrato(triphenylphosphine) derivatives in good yield; the complex “Rh(NO₃) (NO)₂(OPPh₃)₂” is positively identified as [Rh(NO₃)₂ (NO) (PPh₃)₂]     

The structure of hexafluoroacetone azine bis(triphenylphosphine)platinum

The crystal structure of hexafluoroacetone azine bis(triphenylphosphine)platinum, C₄₂H₃₀F₁₂N₂P₂Pt, has been determined by single-crystal X-ray diffraction techniques. The compound crystallizes in the monoclinic space group C2/c with a 31.155(3), b 13.091(1), c 21.828(2) Å, β 109.23(1)° and Z = 8. Manual diffractometer methods (Cu radiation, λ 1.54050 Å) were used to obtain 5046 reflections with I_net ? 8 counts sec^?1 at 21°C. The structure was solved by the heavy atom method and was refined, including CH₂Cl₂ at occupancy 0.4 on a crystallographic 2-fold axis, by block-diagonal least-squares methods to R = 0.056. Location of the phenyl hydrogen atoms was not attempted. The platinum atom is σ-bonded to one CN of the azine ligand forming a $\text{PtCN}$ three-membered ring. Coordination about platinum consists of a slightly distorted square-planar arrangement of the phosphorus atoms and the bonded carbon and nitrogen atoms of the unsaturated ligand. The observed difference in PtP bond lengths is rationalized in terms of the trans-influence.     

cis‐Bis­(dicyan­amido)bis(1,10‐phen­an­throline)­manganese(II) and cis‐bis(dicyan­amido)­bis(1,10‐phen­an­thro­line)­zinc(II)

The title compounds are isomorphous, comprised of neutral monomeric [M(phen)₂(dca)₂] [(I): M = Mn, (II): M = Zn; phen is 1,10‐phenanthroline, C₁₂H₈N₂; dca is dicyan­amide, C₂N₃] mol­ecules. In the mol­ecule, the divalent metal ion is in a distorted octahedral coordination environment formed by six N atoms from the phen and dca ligands. The Mn—N [2.144 (2)–2.319 (2) Å] and Zn—N [2.075 (2)–2.245 (2) Å] distances are in agreement with the difference in size of the two divalent ions.     

Synthesis and coordination properties of palladium(II) and platinum(II) complexes with phosphonated triphenylphosphine derivatives

Two triphenylphosphine derivatives, diethyl [4-(diphenylphosphanyl)benzyl]phosphonate (3a) and tetraethyl {[5-(diphenylphosphanyl)-1,3-phenylene]dimethylene}bis(phosphonate) (3b), and also the corresponding free acids 4a and 4b were prepared. These ligands were characterized by ¹H, ¹³C and ³¹P NMR spectroscopy and mass spectrometry. A full set of their Pd(II) and Pt(II) complexes of the general formula [MCl₂L₂] and one dinuclear complex trans-[Pd₂Cl₄(3a)₂] were synthesized and their isomerization behaviour in solution was studied. The complexes were characterized by ¹H, ¹³C, ³¹P and ¹⁹⁵Pt NMR spectroscopy, mass spectrometry and far-IR spectroscopy. The X-ray structures of all complexes with 3a or 3b have usual slightly distorted square-planar geometry on the metal ion. Salts of phosphonic acids 4a and 4b and their complexes are freely soluble in aqueous solution; therefore, they can be potentially useful in aqueous or biphasic catalysis.