Bond energies and thermal decomposition of [Pt(X)(CH3)(P(C2H5)3)2] complexes

The thermal decomposition of the complexes trans-[Pt(X)(CH₃)L₂] (L  P(C₂H₅)₃; X  Cl, Br, I, CN) in decalin at 170 and 200°C affords methane platinum metal and [Pt(X)₂L₂]. The kinetics of the decomposition of the complexes were determined by monitoring the appearance of methane by GLC. The observed first-order rate constant was found to be independent on the nature of the ligand X. The thermal decomposition of the trideuteriomethyl complexes [Pt(X)(CD₃)L₂] (X  I, CN) in decalin-d₁₈ at 170 and 200°C was studied by GLC/MS. The thermolysis affords CD₃H and CD₄ in ratios which are independent of the nature of X and of the temperature used. The mass spectra of the complexes were also examined. A relative scale of platinum-to-methyl bond dissociation energies has been established by measuring the appearance potential of the fragment ion [Pt(X)L₂]⁺ and the ionization energies in the series [Pt(X)(CH₃)L₂]. Ionization potentials and PtCH₃ bond energies show a clear dependence on the nature of X which is not reflected in corresponding changes in the decomposition rates.     

Synthese et etude des complexes [C5H4(CH2)3C5H4]Ti(C5H5)2 presentant un pont entre deux ligands cyclopentadienyles

The complex (di-η⁵-C₅H₄CH₂CH₂CH₂C₅H₄)Ti(η¹-C₅H₅)₂ (I) can be obtained unambiguously starting from the corresponding bridged titanocene dichloride. Attempts to synthesize the isomeric compounds (η⁵-C₅H₅)₂ Ti(di-η¹-C₅H₄-CH₂CH₂CH₂C₅H₄) (I′) by the action of a convenient bridged dianion on (C₅H₅)₂ TiCl₂ afford several compounds, one of them is the complex I. The possibility of interconversion of these complexes by a fluctional process is discussed.     

Synthesis and reactivity of [N(C6H4Br)3][B(C6F5)4]: the X-ray crystal structure of [Fe(C5H5)2][B(C6F5)4]

A new chemical oxidant [N(4-C₆H₄Br)₃][B(C₆F₅)₄], was prepared and used to synthesize [Fe(C₅H₅)₂][B(C₆F₅)₄]. The crystal structure of [Fe(C₅H₅)₂][B(C₆F₅)₄] was determined.     

Effect of ligands on the thermolysis of the double complexes [Co(NH3)6]2C2O4[Cu(C2O4)2]2 and [Co(NH3)6]Cl[Cu(C7H4O3)2]

The thermolysis of the complexes [Co(NH₃)₆]₂C₂O₄[Cu(C₂O₄)₂]₂ (I) and [Co(NH₃)₆]Cl[Cu(C₇H₄O₃)₂] (II) in air and hydrogen at 200, 350, and 500°C and the composition and properties of the thermolysis products are considered. The oxidative thermolysis of the complexes yields mixtures of cobalt and copper oxides, including mixed ones. The reductive thermolysis of the complexes yields a Co + Cu bimetallic powder in the case of compound I and a Co + Cu + C powder in the case of compound II. The thermal behavior of the complexes is governed by the nature of the ligand coordinated to the copper atom. The observed data are explicable in terms of the properties of this ligand. The chemistry of the oxidative and reductive thermolysis is discussed. Original Russian Text ? D.P. Domonov, S.I. Pechenyuk, N.L. Mikhailova, A.T. Belyaevskii, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 7, pp. 1104–1110.     

The Cu(I) thiocyanate complexes with N-allylquinolinium: Synthesis and crystal structures of [C9H7NC3H5]Cu(SCN)2 and [C9H7NC3H5]Cu2(SCN)3

The crystals of [C₉H₇NC₃H₅]Cu(SCN)₂ (I) and [C₉H₇NC₃H₅]Cu₂(SCN)₃ (II) were obtained in the reaction of N-allylquinolinium bromide with CuSCN and NH₄SCN in a methanol solution. The crystals of I are triclinic: space group P , Z = 2, a = 8.619(2), b = 8.755(2), c = 10.463(3) ?, α = 77.18(3), β = 69.95(3), γ = 79.38(3)°, V = 718.1(3) ?³. The crystals of II are opthorhombic: space group P2₁2₁2₁, Z = 4, a = 5.744(2), b = 16.799(4), c = 17.980(5), V = 1735.9(9) ?³. The structure of compound I is built of infinite linear {Cu(SCN)₂⁻}_∞ anions and the N-allylquinolinium cations bonded additionally by relatively weak hydrogen contacts C-H...S. The [C₉H₇NC₃H₅]⁺ cations are located between the corrugated layers of the {Cu₂(SCN)₃⁻}_∞ anions in compound II. As in the case of the previously studied copper(I) halide complexes, the C=C bond of the allyl group in the N-allylquinolinium cation of complexes I, II does not interact with Cu(I). Original Russian Text ? A.V. Pavlyuk, V. Kinzhybalo, T. Lis, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 10, pp. 764–769.     

Synthesis and crystal structures of (C8h8)Nd(C5H9C5H4) (THF)2 and [(C8H8)Gd(C5H9C4H4(THF)][(C8H8)GD(C5H9C5H4(THF)2]

LnCl₃ (Ln=Nd, Gd) reacts with C₅H₉C₅H₄Na (or K₂C₈H₈) in THF (C₅H₉C₅H₄ = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C₅H₉C₅H₄)LnCl₂(THF)_n (orC₈H₈)LnCl₂(THF)_n], which further reacts with K₂C₈H₈ (or C₅H₉C₅H₄Na) in THF to form the litle complexes. If Ln=Nd the complex (C₈H₈)Nd(C₅H₉C₅H₄)(THF)₂ (a) was obtained: when Ln=Gd the 1 : 1 complex [(C₈H₈)Gd(C_%H₉)(THF)][(C₈H₈)Gd(C₅H₉H₄)(THF)₂] (b) was obtained in crystalline form.

The crystal structure analysis shows that in (C₈H₈)Ln(C₅H₉C₅H₄)(THF)₂ (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η⁵), cyclooctatetraenyl (η⁸) and two oxygen atoms from THF are coordinated to Nd³⁺ (or Gd³⁺) with coordination number 10.

The centroid of the cyclopentadienyl ring (Cp′) in C₅H₉C₅H₄ group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd³⁺ (or Gd³⁺). In (C₈H₈)Gd(C₅H₉C₅H₄)(THF), the cyclopentyl-cyclopentadienyl (η⁵), cyclooctatetraenyl (η⁸) and one oxygen atom are coordinated to Gd³⁺ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd³⁺, which is almost in the plane (dev. -0.0144 Å).     

Three-coordinate RhX[P(C6H11)3]2, their reactions with N2 and O2, and the trans-influence in RhX[P(C6H11)3]2L (X = anionic,L = neutral ligand)

Three-coordinate RhX(PCy₃)₂ complexes (X = F, Cl, Br, I; Cy = cyclohexyl) have been prepared from rhodium(I) cyclooctene compounds. RhCl(PCy₃)₂ is in equilibrium with its dimer. The complexes RhX(PCy₃)₂ (X = Cl, Br, I) form the adducts RhX(PCy₃)₂(N₂) with dinitrogen, the times for N₂-fixation being 4 days, 3 hours and 15 minutes respectively. The three-coordinate complexes form four-coordinate dioxygen adducts RhX(PCy₃)₂(O₂) which have unusually high ν(OO) at about 990 cm^?1. This high frequency is attributed to the four-coordination, which is exceptional for dioxygen complexes. From RhF(PCy₃)₂ carbonyl, ethene, and diphenylacetylene complexes RhX(PCy₃)₂L (X = F, Cl, Br, I, N₃, NCO, NCS; L = CO, C₂H₄, C₂Ph₂) (X = CN, NO₃, acetate; L = CO) have been prepared. The trans-influence of the anionic ligands on the infrared frequencies of the neutral ligands is discussed in terms of the different π-bonding properties of the X- and L-ligands.     

Hydrothermal synthesis and characterization of a new 3D vanadium(III) phosphite (C4H8N2H4)0.5(C4H8N2H3)[V4(HPO3)7(H2O)3]1.5H2O

A new vanadium(III) phosphite, (C₄H₈N₂H₄)_0.5(C₄H₈N₂H₃)[V₄(HPO₃)₇(H₂O)₃]1.5H₂O, has been synthesized hydrothermally by using V₂O₅, H₃PO₃ as reactants, piperazine as the structure-directing agent. The as-synthesized product was characterized by powder X-ray diffraction, IR spectroscopy, inductively coupled plasma analysis, thermogravimetric analysis, and SQUID magnetometer. Single-crystal X-ray diffraction analysis shows that the title compound crystallized in the trigonal space group (No. 165) with the parameters: , , and Z=4. Its structure is built up by alternation of octahedral VO₆ or VO₅(H₂O) and pseudo-pyramidal HPO₃ units to form infinite 2D layers, and these layers are interconnected by sharing vertex-oxygen with octahedral VO₆ units to generate a 3D open-framework structure with 12-membered ring channels in a and b directions, respectively, where there exist entrapped diprotonated and mono-protonated piperazine cations, and water molecules. Magnetic measurement indicates that paramagnetic behavior is observed down to 4 K.     

The crystal and molecular structure of dicarbonylbis(diphenylethylphosphine) platinum(0) Pt(CO)2[P(C6H5)2(C2H5)]2

The complex dicarbonylbis(diphenylethylphosphine)platinum, Pt(CO)₂[P(C₆H₅)₂(C₂H₅)]₂, crystallizes in either of the enantiomorphous space groups P3₁21 (No. 152) and P3₂21 (No. 154) with cell dimensions a = 10.64(1), c = 22.06(1) Å, U = 2163 ų; p_c = 1.564 g/cm³ for Z = 3, p_m = 1.55(3) g/cm³. The intensities of 1177 independent reflections have been determined by counter methods with MoKα monochromatized radiation. The structure has been solved by the heavy atom method. The refinement, carried out by full-matrix least squares down to a final R factor of 0.042, has enabled the absolute configuration of the crystal sample (space group P3₁21) to be ascertained. The molecule is roughly tetrahedral, and has the metal atom lying on a two-fold axis of the cell. Bond parameters are: PtC = 1.92(2) Å, PtP = 2.360(4) Å, CPtC = 117(1)° and PPtP = 97.9(2)°. The PtC₂ and PtP₂ moieties make a dihedral angle of 86.0(3)°. The overall C₂ symmetry of the molecule is probably only a statistically averaged situation, a disorder in the PtCO interactions being apparent from the orientations of the thermal ellipsoids of the C and O atoms.     

1-Allyl derivatives: Synthesis and crystal structures for [(NH2C5H4N(C3H5))2Cu3Cl3(NO3)2] and [C9H7N(C3H5)Cu(NO3)2]

1-Allyl-4-aminopyridinium chloride reacts with Cu(NO₃)₂ · 3H₂O in an ethanolic solution under the conditions of ac electrochemical synthesis at copper electrodes to form crystals of compound [(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂] (I). The crystals of compound I are monoclinic: space group P2₁/c, Z = 4, a = 25.770(7), b = 7.230(4), c = 12.505(5) ?, β = 92.58(3)°, V = 2328(2) ?³. The direct interaction of 1-allylquinolinium nitrate with Cu(NO₃)₂ · 3H₂O in a methanolic solution in the presence of metallic copper yields crystals of compound [C₉H₇N(C₃H₅)Cu(NO₃)₂] (II). The crystals of compound II are triclinic: space group P , a = 6.756(3), b = 8.391(4), c = 12.489(5) ?, α = 77.18(3)°, β = 89.48(4)°, γ = 73.32(3)°, V = 662.0(5) ?³. The structure of compound I is built of infinite linear anions: polymeric fragments {(NH₂C₅H₄N(C₃H₅))₂Cu₃Cl₃(NO₃)₂} _n . Each of two copper atoms (Cu(1) and Cu(2)) π-coordinates the C=C bonds of the allyl groups of the 1-allyl-4-aminopyridinium cations, the oxygen atom of the nitrate ions, and two chlorine atoms. The third copper atom Cu(3) is linearly linked with two chlorine atoms. Particular polymeric fragments are additionally joined by the N-H…O, C-H…O, C-H…Cl hydrogen bonds. The crystal structure of compound II is built-up of the isolated L₂Cu₂(NO₃)₄ fragments (L is the 1-allylquinolinium cation). The metal atom is localized in the trigonal pyramidal coordination environment of three oxygen atoms of the nitrate ions and of the C=C bond of the allyl group of the cation. The particular L₂Cu₂(NO₃)₄ fragments are additionally joined by the C-H…O hydrogen bonds. Original Russian Text ? A.V. Pavlyuk, T. Lis, M.G. Mys’kiv, 2009, published in Koordinatsionnaya Khimiya, 2009, Vol. 35, No. 6, pp. 458–462.     

Etude vibrationnelle des composes (C4H4P)Mn(CO)3 et [C4H2(CH3)2P]Mn(CO)3 et calcul du champ de force du cycle C4H4P complexe

The Raman and infrared spectra (4000200 cm^?1) of (C₄H₄P)Mn(CO)₃ and (C₄D₄P)Mn(CO)₃, and of [C₄H₂(CH₃)₂P]Mn(CO)₃ and [C₄D₂(CH₃)₂P]Mn(CO)₃ in the liquid and solid states (10–400 K) have been investigated. A complete vibrational assignment is proposed and valence force fields of the (C₅H₅) and (C₄H₄P) cycles are compared. From these results, it is clearly shown that the (C₄H₄P) rings are more electrophilic and weaker π-electron donors than (C₅H₅) rings, this is in agreement with their chemical behavior.     

Paramagnetic products of [Ni (C4H6)2]n interaction with diethylaluminium chloride

ESR method has been used to identify metastable Ni⁺ complexes in toluene solution formed by the interaction of [Ni(C₄H₆)₂] with Et₂AlCl. Reversible changes in the ground state of Ni⁺ ions after the introduction of supplementary neutral ligands (PPh₃, C₂H₄) into the system have been established.

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Ni⁺ , [Ni (C₄H₆)₂]_n c Et₂AlCl. Ni⁺ (PPh₃, C₂H₄) .

     

The evaluation of singlet-triplet separations for [W2(μ-H)(μ-Cl)Cl4(μ-dppm)2] and [W2(μ-H)2 (μ-O2CC6H5)2(P(C6H5)3)2] based on P NMR and crystallographic data

The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W₂(μ-H)(μ-Cl)(Cl₄(μ-dppm)₂ · (THF)₃ (II) has been studied by ³¹P NMR spectroscopy. The structural characterization of [W₂(μ-H)₂(μ-O₂CC₆H₅)₂Cl₂(P(C₆H₅)₃)₂] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W₂(μ-H)(μ-Cl)Cl₄(μ-dppm)₂ · (THF)₃] (II), has been synthesized and the value of −2J determined from variable-temperature ³¹P NMR spectroscopy.     

The crystal structure of tetrakis(methyldiphenylphosphine)iridium(I) tetrafluoroborate with cyclohexane of solvation: Ir[P(C6H5)2CH3]4BF4 - C6H12

The crystal structure of tetrakis(methyldiphenylphosphine)iridium(I) tetrafluoroborate with cyclohexane of solvation, [Ir(PPh₂Me)₄]BF₄·C₆H₁₂, has been determined from a three-dimensional X-ray analysis. The compound has been analysed in space group C₂/c of the monoclinic system. There are twelve molecules (i.e. 1.5 molecules per asymmetric unit) in a cell of dimensions a = 36.804(8), b = 22.93(2), c = 21.676(4) Å, β = 121.41(1)°. Block-diagonal least-squares refinement has given a final R-factor of 0.060 for 7905 reflections having I > 3σ(I).The structure consists of two crystallographically distinct, but structurally similar molecules, one on a general position and one on a crystallographic two-fold axis. The phosphine ligands around the iridium atoms are in a very distorted square-planar arrangement. The reactions of the cation axe discussed in terms of this structure.     

Crystal Structure of (H3O)4[(C2H5)4N]6 [Th2Cl4(H2O)12O]3[Re4Se4(CN)12]4

Crystals of the rhenium cluster complex (H₃O)₄[(C₂H₅)₄N]₆[Th₂Cl₄(H₂O)₁₂O]₃[Re₄Se₄(CN)₁₂]₄ are obtained in an acidic (HCl) aqueous solution by the reaction of cluster salt K₄[Re₄Se₄(CN)₁₂]·6H₂O with ThCl₄ and (C₂H₅)₄NCl. Single crystal X-ray analysis shows that the title compound is ionic and crystallizes in the cubic crystal system (a = 22.7322(3) ?, V = 11746.93(27) ?³, Z = 2, I4 3m space group, R = 0.0350). It contains [Th₂Cl₄(H₂O)₁₂O]²⁺ cations with two thorium atoms bonded to each other through the bridging oxygen atom forming an angle of 180° in the structure.     

The electronic structure of bis(o-phenylenediamido)nickel,Ni[C6H4(NH)2]2

Extended Hückel and multiple scattering Xα calculations are reported for the title complex. Both sets of results are in quantitative agreement, suggesting that part of the unusual spectral and electrochemical properties of this system may be ascribed to the predominantly ligand character of the HOMO and LUMO orbitals.     

三维异核Mn-Na配合物[MnNa(N3)4(C5H5N)4]的合成与表征

Azide-containing coordination polymers have received considerable attention for the construction of new molecule-based magnets. A three dimensional heteronuclear Mn-Na compound [MnNa(N₃)₄(C₅H₅N)₄] was obtained by reaction of [Mn₃O(O₂CCH₃)₆(py)₃]ClO₄ and NaN₃ in pyridine solvents. The title compound crystallizes in monoclinic space group C2/c, a=1.536 6(2), b=1.045 3(2), c=1.576 3(2) nm, β=90.309(3)°, V=2.531 8(6) nm³, Z=4. In the structure, each Mn³⁺ and Na⁺ ion coordinated with four N atoms from four N₃^- and two N atoms from two pyridine molecules. Each pair of Mn³⁺ and Na⁺ ion are linked by N₃^- bridges into a 3D polymer with PtS topology. CCDC: 706250.     

Crystal and molecular structures of the Rh[(C2H5O)2PS2]3 and Co[(C6H5O)2PS2]3 chelate compounds

The crystal structures of the Rh[(EtO)₂PS₂]₃ (I) and Co[(PhO)₂PS₂]₃ (II) chelate compounds were determined from X-ray diffraction (XRD) data (CAD-4 diffractometer, MoK _β radiation, 1193 F _hkl , R = 0.0516 for I and 513 F _hkl , R = 0.0305 for II). Crystals I are monoclinic: a = 14.233(3) Å, b = 13.570(3) Å, c = 14.272(3) Å; β = 90.66(3)°, V = 2756.3(10) ų, Z = 4, ρ_calc = 1.587 g/cm³, space group C2/c. Crystals II are trigonal: a = 15.149(2) Å, c = 30.306(6) Å; V = 6023.2(16) ų, Z = 6, ρ_calc = 1.493 g/cm³, space group R3ˉ. Structures I and II consist of discrete mononuclear molecules. The coordination polyhedra of the M atoms (M = Rh, Co) are distorted octahedra formed by six sulfur atoms of three cyclic bidentate (RO)₂ PS₂⁻ ligands. Original Russian Text Copyright ? 2008 by R. F. Klevtsova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 2, pp. 330–334, March–April, 2008.     

Synthesis and crystal structure of Ir(C2H4)2(C5H7O2)

We report a new synthesis and characterization of Ir(C₂H₄)₂(C₅H₇O₂) [(acetylacetonato)-bis(η²-ethene)iridium(I)], prepared from (NH₄)₃IrCl₆ · H₂O in a yield of about 45%. The compound has been characterized by X-ray diffraction crystallography, infrared, Raman, and NMR spectroscopies and calculations at the level of density functional theory. Ir(C₂H₄)₂(C₅H₇O₂) is isostructural with Rh(C₂H₄)₂(C₅H₇O₂), but there is a substantial difference in the ethylene binding energies, with Ir-ethylene having a stronger interaction than Rh-ethylene; two ethylenes are bound to Ir with a binding energy of 94 kcal/mol and to Rh with a binding energy of 70 kcal/mol.     

C2H3Cl分子团簇内部离子-分子反应产生C4H5Cl+的研究

用同步辐射对（Ｃ２Ｈ３Ｃｌ）２分子团簇进行了光电离研究，发现该团簇内部发生了离子－分子化学反应，生成了十分稳定的反应产物Ｃ４Ｈ５Ｃｌ＾＋，不再是ｖａｒｄｅｒＷａａｌｓ弱键络合物，本文对反主尖机理进行了初步探讨。