Synthesis and structure of platinum complexes [Ph4P]+[PtCl3(DMSO)]− and [Ph4P]+[PtCl5(DMSO)]−

The reaction of tetraphenylphosphonium chloride with an equimolar amount of potassium tetrachloroplatinate or hexachloroplatinic acid in dimethyl sulfoxide gave the complexes [Ph₄P]⁺[PtCl₃(DMSO)]^? (I) and [Ph₄P]⁺[PtCl₅(DMSO)]^? (II), respectively. The phosphorus atoms in the cations have tetrahedral environment, the CPC angles and P-C distances 105.63(13)°–112.13(14)°, 1.795(3)–1.797(3) Å I) and 105.7(3)°–112.9(3)°, 1.783(7)–1.791(6) Å II). The platinum coordination polyhedra in the anions [PtCl₃(DMSO)]^? and [PtCl₅(DMSO)]^? are distorted square (Pt-S, 2.1937(8); Pt-Cl, 2.2894(10)–2.3024(10) Å; trans-angles: SPtCl, 177.38(4)°; ClPtCl, 175.40(4)°) and octahedron (Pt-S 2.291(2) Å; Pt-Cl, 2.312(2)–2.334(2) Å, trans-angles: SPtCl, 178.28(9)°; ClPtCl, 178.80(9)° and 178.88(8)°).     

Synthesis and structure of osmium complexes [Ph3PR]2[OsCl6]·4DMSO

Russian Journal of General Chemistry - Reaction of sodium hexachloroosmate(IV) dihydrate with (2-oxopropyl)- and (2-carboxyethyl)-triphenylphosphonium chlorides in dimethyl sulfoxide afforded...     

Synthesis and structure of palladium complexes [Ph3PhCH2P]+[PdCl3(DMSO)]− · DMSO, [Ph4P]+[PdCl3(DMSO)]−, and [Ph4Sb(DMSO)]+[PdCl3(DMSO)]−

[Ph₃PhCH₂P]⁺[PdCl₃(DMSO)]^? · DMSO (I), [Ph₄P]⁺[PdCl₃(DMSO)]^? (II), and [Ph₄Sb(DMSO)]⁺[PdCl₃(DMSO)]^? (III) complexes have been synthesized via the reaction of palladium chloride with equimolar amounts of triphenylbenzylphosphonium chloride, tetraphenylphosphonium chloride, and tetraphenylstibonium chloride, respectively. According to X-ray diffraction data, the cations of complexes I (CPC = 104.90(8)°–111.61(9)°) and II (CPC = 105.12(10)°–111.46(10)°) have slightly distorted tetrahedral structures with P-C bond lengths of 1.786(2)–1.809(2) and 1.791(2)–1.799(2) Å, respectively. The antimony atom in the [Ph₄Sb(DMSO)]⁺ cation has a trigonal bipyramidal surrounding with the dimethyl sulfoxide (DMSO) oxygen atom in an axial position (Sb...O 2.567(2) Å). The palladium atoms in the square mononuclear anions of complexes I, II, and III are tetracoordinate, and Pd-Cl distances are 2.3101(5)–2.3104(5) Å, 2.2950(7)–2.2038(7) Å, and 2.2986(9)–2.3073(9) Å, respectively. The DMSO ligands are coordinated to the palladium atom through the sulfur atom (Pd-S, 2.2318(5) (I), 2.2383(6) (II), and 2.2410(9) Å (III)).     

Synthesis,crystal structure and luminescent properties of two complexes containing [Au(CN)2] − building blocks

Two supramolecular complexes, {{Ni(H₂O)(phen)₂[Au(CN)₂]}[Au(CN)₂]?·?1.5H₂O} _n (1) (phen?=?1,10-phenanthroline) and [H₂teta][Au₂(CN)₄]?·?2H₂O (2) (teta?=?5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyocloteradeca-4,11-diene) have been synthesized and structurally characterized. Complex 1 was a one-dimensional infinite chain constructed by [Au(CN)₂]^? building blocks. In complex 2, there are one cation, one anion, and two water molecules in the asymmetric unit. The two complexes are interconnected through a combination of aurophilic attractions and hydrogen bonds and formed into 3D supramolecular structures. The aqueous solutions of 1 and 2 display interesting luminescence at room temperature.     

Synthesis and structure of bismuth-containing complexes [(Ph4BiO)2{2,5-(CH3)2C6H3S(O)}] 2 + [Ph2Bi2I6]2−,[(Ph4Bi]+[PhBi(C5H5N)I3]−, [Ph4Sb] 4 + [Bi4I16]4−⋅2(CH3)2 C=O, and [Ph4Sb] 3 + [Bi5I18]3−

The reactions of tetraphenylbismuthonium and -stibonium salts Ph₄EX (E = Bi, Sb; X = I, OSO₂ (C₆H₃(CH₃)₂-2,5), OSO₂C₆H₃(OH-4)(COOH-3)) with bismuth triiodide in acetone afford complexes [Ph₄Bi]⁺[PhBi(C₅H₅N)I₃]^-, [(Ph₄BiO)₂S(O){2,5-(CH₃)₂C₆H₃S(O)} [Ph₂Bi₂I₆]^2–, [Ph₄Sb [Bi₄I₁₆]^4-·2(CH₃)²C=O, and [Ph₄Sb] ₃₊ ⁺ [Bi₅I₁₈]^3-, whose structural units, according to the X-ray diffraction data, are tetraphenylbismuthonium (-stibonium) cations and mono-, di-, tetra-, and pentanuclear anions, respectively.     

Synthesis and Structure of Acetonitrile Solvates of Copper(II) Monofluoroacetate and Silver(I) Trifluoroacetate, [Cu2(CH2FCOO)4· 2CH3CN](CH3CN) and Ag3(CF3COO)3(CH3CN)2

Compounds [Cu₂(CH₂FCOO)₄· 2CH₃CN](CH₃CN) (I) and Ag₃(CF₃COO)₃(CH₃CN)₂(II) were synthesized and studied by X-ray structural analysis. Crystals Iare monoclinic, space group C2/c, a= 27.854(6), b= 8.286(2), c= 19.428(4) Å, = 106.82(3)°, V= 4292(2) ų, Z= 8, R ₁= 0.0426; crystals IIare triclinic, space group , a= 8.676(2), b= 9.819(2), c= 11.961(2) Å, = 95.27(3), = 109.59(3)°, = 104.60(3)°, V= 911.4(3) ų, Z= 2, R ₁= 0.0252. Structure Iis composed of the structural units (lanterns) typical of copper(II) carboxylates. The presence of an additional acetonitrile molecule noncoordinated by the copper atoms makes it possible to consider compound Ias a lattice clathrate. Structure IIhas no analogs among the silver carboxylates. It simultaneously contains silver atoms with coordination numbers varying from 2 to 4.     

Synthesis, crystal structure, magnetic property and thermal studies of [Ni(CH(3)COO)2·(NH2CH2Ph)4

[Ni(CH(3)COO)(2)·(NH(2)CH(2)Ph)(4)] complex was synthesized using benzylamine and nickel acetate. The molecular structure of this complex was obtained by single crystal X-ray diffraction and characterized by elemental analysis, IR spectrometry and thermal analysis. The complex crystallized in the monoclinic space group P2(1)/n with cell parameters a=11.234(4)?, b=6.459(2)?, c=22.647(8)?, α=90.00, β=91.149(4)°, γ=90.00, V=1642.8(10)?(3), Z=2. The structure has been solved by direct methods and refined to R(1)=0.0876 for 6377 observed reflections I>2σ(I). Magnetic studies for complex show the data over the whole temperature range 5-300 K are well fitted to the Curie-Weiss law with C=1.03 cm(3) K mol(-1) and θ=-1.38 K. This fitting indicates antiferromagnetic interaction between the Ni ions and the metal center exhibits distorted octahedral coordination geometries. The thermal analysis was carried out to understand the thermal stability of the title complex.     

Synthesis and structure of the dimeric organo-antimony (V) imido complex [Ph3Sb(μ-NCH2CH2Ph)]2

The amine PhCH₂CH₂NH₂ undergoes dimetallation by [Ph₃Sb(NMe₂)₂] (1) under mild conditions to give the first structurally authenticated example of an organo-Sb(V) imido complex, [Ph₃Sb(μ-NCH₂CH₂Ph)]₂ (2).     

Syntheses,structures and properties of two complexes bridged by [M(CN)2] − (M = Ag (I), Au (I))

A dinuclear complex Cu₂(bpca)₂(H₂O)₂(Ag₂(CN)₃) (1) and a 1D complex [Cu₂(bpca)₂(H₂O)₂(Au(CN)₂)₂] _n (2) (bpca = bis(2-pyridylcarbonyl)amide anion) have been prepared, structurally characterized and 2 has been magnetically characterized. The magnetic properties show an antiferromagnetic interaction between the two Cu(II) ions. Based on the Hamiltonian ? = ?2J Σ (S_i · S_{i +1}), best fitting for the experimental data leads to J = ?0.045 cm^?1.     

Synthesis and characterization of (RPh3P)3[Bi3I12] (R = Me,Ph) iodobismuthate complexes for photocatalytic degradation of organic pollutants

Research on Chemical Intermediates - Phosphonium iodobismuthates(III) (MePh3P)3[Bi3I12] (1) and (Ph4P)3[Bi3I12] (2) were prepared, and X-ray crystal structures were determined for both complexes....     

Synthesis and structure of antimony iodide complexes: [Ph3MeP] + 2 [SbI5]2−, [Ph3MeP] + 3 [Sb3I12]3−·Me2C=O, [Ph3MeP] + 3 [Sb3I12]3−, and [Ph3MeP] + 3 [Sb2I9]3−

Complexes with antimony-containing anions, [Ph₃MeP] ₊ ² [SbI₅]^2? (I), [Ph₃MeP] ₊ ² [Sb₃I₁₂]^3? (II), [Ph₃MeP] ₊ ³ [Sb₃I₁₂]^3? · Me₂C=O (III), and [Ph₃MeP] ₊ ³ [Sb₂I₉]^3? (IV), were synthesized by reacting triphenylmethylphosphonium iodide with antimony iodide. The central atom in the cations of the complexes has a distorted tetrahedral coordination. In the trinuclear anions of complexes II and III, each of the terminal SbI₃ groups is bound to the central Sb atom through two μ₂- and one μ₃ iodine bridges (SbSbSb angles are 103.0° and 102.2°, respectively). In the binuclear anion of complex IV, antimony atoms are linked with each other via three bridging iodine atoms.     

Conductivity and Redox Potentials of Ionic Liquid Trihalogen Monoanions [X3]−, [XY2]−, and [BrF4]− (X=Cl,Br, I and Y=Cl,Br)

The ionic liquid (IL) trihalogen monoanions [N₂₂₂₁][X₃]⁻ and [N₂₂₂₁][XY₂]⁻ ([N₂₂₂₁]⁺=triethylmethylammonium, X=Cl, Br, I, Y=Cl, Br) were investigated electrochemically via temperature dependent conductance and cyclic voltammetry (CV) measurements. The polyhalogen monoanions were measured both as neat salts and as double salts in 1-butyl-1-methyl-pyrrolidinium trifluoromethane-sulfonate ([BMP][OTf], [X₃]⁻/[XY₂]⁻ 0.5 M). Lighter IL trihalogen monoanions displayed higher conductivities than their heavier homologues, with [Cl₃]⁻ being 1.1 and 3.7 times greater than [Br₃]⁻ and [I₃]⁻, respectively. The addition of [BMP][OTf] reduced the conductivity significantly. Within the group of polyhalogen monoanions, the oxidation potential develops in the series [Cl₃]⁻>[BrCl₂]⁻>[Br₃]⁻>[IBr₂]⁻>[ICl₂]⁻>[I₃]⁻. The redox potential of the interhalogen monoanions was found to be primarily determined by the central halogen, I in [ICl₂]⁻ and [IBr₂]⁻_, and Br in [BrCl₂]⁻. Additionally, tetrafluorobromate(III) ([N₂₂₂₁]⁺[BrF₄]⁻) was analyzed via CV in MeCN at 0 °C, yielding a single reversible redox process ([BrF₂]⁻/[BrF₄]⁻).     

Synthesis and equilibrium binding studies of cationic, two-coordinate gold(I) π-alkyne complexes

Reaction of a 1:1 mixture of (L)AuCl [L = P(t-Bu)₂o-biphenyl or IPr] and AgSbF₆ with internal alkynes led to isolation of the corresponding cationic, two-coordinate gold π-alkyne complexes in ≥ 90% yield. Equilibrium binding studies show that the binding affinities of alkynes to gold(I) are strongly affected by the electron density of the alkyne and to a lesser extent on the steric bulk of the alkyne. These substituent effects on alkyne binding affinity are greater than are the differences between the inherent binding affinities of alkynes and alkenes to gold(I).     

Octahedral cluster Mo complexes (Bz3NH)3[Mo6OCl13] and (Bz3NH)2[Mo6Cl14] · 2CH3CN: Synthesis, crystal structure and properties

The salts (Bz₃NH)₃[Mo₆OCl₁₃] (I) and (Bz₃NH)₂[Mo₆Cl1₄] · 2CH3CN (II) were obtained by reacting melted tribenzylamine with cluster Mo compounds. Compound II contains a known cluster anionic complex [Mo₆Cl₁₄]^2?. Compound I includes novel cluster anionic complex [Mo₆OCl₁₃]^3?, where one internal Cl atom is replaced by the O atom. Complex II exhibits phosphorescence in a long-wavelength region of visible spectrum.     

Synthesis and structure of novel dinitrosyl iron complexes [Fe2(μ-SCH2CH2NHR)2(NO)4]

Two novel dinitrosyl iron complexes with thiolate bridging ligands [Fe₂(μ-SCH₂CH₂NHR)₂(NO)₄] (R = Ac, Boc), derived from the cysteamine complex [Fe₂(μ-SCH₂CH₂NH₃)₂(NO)₄]²⁺ are described. The complex with acylated cysteamine is characterized by X-ray diffraction analysis. The cysteamine complex is a convenient precursor for modification of the bridging ligand.     

Synthesis, Characterization, and Physical Properties of Two Trinuclear, Mixed-Valence Species of Type [μ3-OMnIIMnIII 2(O2CCF3)6(R)3] (R=H2O, CH3COOH)

The preparation and characterization of two new mixed-valence, trinuclear species, [Mn₃O(O₂CCF₃)₆(H₂O)₃]CF₃COOH4/3H₂O (1) and [Mn₃O(O₂CCF₃)₆(CH₃COOH)₃] (2), is reported. Compound 1 crystallizes in the triclinic space group, P¯1 (No. 2), with the parameters, a=12.3131(9) Å, b=12.4427(9) Å, c=12.965(1) Å, =72.593(4)°, =73.453(5)°, =68.345(4)°, V=1727.2(2) ų, and Z=2. A total of 14060 reflections were collected in the range 1.6827.52°. The final weighted and non-weighted agreement indices, R1=0.0589 and wR2=0.1445 were based on a total of 6953 unique reflections with an R _int value of 0.0542. Compound 2 crystallizes in the monoclinic space group, P2₁/n (No. 14), with the parameters, a=12.876(3) Å, b=12.212(4) Å, c=17.732(4) Å, =100.40(3)°, V=3640.4(1) ų, and Z=4. A total of 32197 reflections were collected in the range 1.7227.13°. The final weighted and non-weighted agreement factors, R1=0.0647 and wR2=0.1609 were based on a total of 8018 unique reflections with an R _int value of 0.0462. An investigation of the physical properties revealed that both compounds display an intermediate ground state of S=3/2 as a consequence of intramolecular antiferromagnetic coupling. The magnetic data for compound 1 was best fit to the parameters g=2.09, J=–5.5 cm^–1, J=–3.4 cm^–1, and D _Mn(III)=–4.5 cm^–1; the data for compound 2 was best fit to the parameters g=2.10, J=–2.9 cm^–1, J=–5.5 cm^–1, and D _Mn(III)=–4.5 cm^–1.     

Synthesis and crystal structure of a novel mercapto-organotin complex:[Et3NH][Ph2SnCl(μ2-SCH2COO-)]

A novel complex[Et₃NH][Ph₂SnCl(μ²-SCH₂COO-)],has been unexpectedly obtained by the reaction of Ph₃SnCl and HSCH₂COOH in 2:1 molar ratio in the presence of organic base Et₃N.