Ruthenium(II)-Phthalocyaninate(2–): Darstellung und Eigenschaften von Acido(carbonyl)phthalocyaninato(2–)ruthenat(II), [Ru(X)(CO)Pc2−]− (X = Cl,Br, I,NCO, NCS,N3)

Ruthenium(II) Phthalocyaninates(2–): Synthesis and Properties of (Acido)(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) (ⁿBu₄N)[Ru(OH)₂Pc^2?] is reduced in acetone with carbonmonoxid to blue-violet [Ru(H₂O)(CO)Pc^2?], which yields in tetrahydrofurane with excess (ⁿBu₄N)X acido(carbonyl)phthalocyaninato(2–)ruthenate(II), [Ru(X)(CO)Pc^2?]^? (X = Cl, Br, I, NCO, NCS, N₃) isolated as red-violet, diamagnetic (ⁿBu₄N) complex salt. The UV-Vis spectra are dominated by the typical π-π* transitions of the Pc^2? ligand at approximately 15100 (B), 28300 (Q₁) und 33500 cm^?1 (Q₂), only fairly dependent of the axial ligands. v(C? O) is observed at 1927 (X = I), 1930 (Cl, Br), 1936 (N₃, NCO) 1948 cm^?1 (NCS), v(C? N) at 2208 cm^?1 (NCO), 2093 cm^?1 (NCS) and v(N? N) at 2030 cm^?1 only in the MIR spectrum. v(Ru? C) coincides in the FIR spectrum with a deformation vibration of the Pc ligand, but is detected in the resonance Raman(RR) spectrum at 516 (X = Cl), 512 (Br), 510 (N₃), 504 (I), 499 (NCO), 498 cm^?1 (NCS). v(Ru? X) is observed in the FIR spectrum at 257 (X = Cl), 191 (Br), 166 (I), 349 (N₃), 336 (NCO) and 224 cm^?1 (NCS). Only v(Ru? I) is RR-enhanced.     

Tris(2‐methylphenyl)phosphonium tetrachloroborate

The title compound, C₂₁H₂₂P⁺·BCl₄^?, is the first structurally characterized example of the [HP(o‐tolyl)₃]⁺ cation, presented here with BCl₄^? as the counter‐ion. The cation has a near‐tetrahedral P atom and the BCl₄^? anion is near‐tetrahedral at boron. There are no unusually short cation–anion contacts.     

Phosphanimin- und Phosphaniminato-Komplexe von Bor. Synthese und Kristallstrukturen von [BF3(Me3SiNPEt3)], [BCl2(NPPh3)]2, [BCl2(NPEt3)]2, [B2Cl3(NPEt3)2]+BCl4− und [B2Cl2(NPiPr3)3]+BCl4−

Phosphaneimine and Phosphoraneiminato Complexes of Boron. Synthesis and Crystal Structures of [BF₃(Me₃SiNPEt₃)], [BCl₂(NPPh₃)]₂, [BCl₂(NPEt₃)]₂, [B₂Cl₃(NPEt₃)₂]⁺BCl₄^?, and [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? The title compounds have been prepared from the corresponding silylated phosphaneimines and boron trifluoride etherate and boron trichloride, respectively. The compounds form white moisture sensitive crystals, which were characterized by ¹¹B-nmr-spectroscopy, IR-spectroscopy and by crystal structure determinations. [BF₃(Me₃SiNPEt₃)] : Space group P2₁/c, Z = 4, R = 0.032 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1361.0, b = 819.56, c = 1422.5 pm, β = 109.86°. The donor acceptor complex forms monomeric molecules with a B? N bond length of 157.8 pm. [BCl₂(NPPh₃)]₂ · 2 CH₂Cl₂ : Space group P2₁/c, Z = 2, R = 0.049 for reflections with I > 2σ(I). Lattice dimensions at ?50°C: a = 1184.6, b = 2086.4, c = 843.0 pm, β = 96.86°. The compound forms centrosymmetric dimeric molecules in which the boron atoms are linked to B₂N₂ four-membered rings with B? N distances of 152.7 pm via μ₂-N bridges of the NPPh₃ groups. [BCl₂(NPEt₃)]₂ : Space group Pbca, Z = 4, R = 0.029 for reflections with I > 2σ(I). Lattice dimensions at ?90°C: a = 1269.5, b = 1138.7, c = 1470.3 pm. The compound has a molecular structure corresponding to the phenyl compound with B? N ring distances of 151.0 pm. [B₂Cl₃(NPEt₃)₂]⁺BCl₄^? : Space group Pbca, Z = 8, R = 0.034 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1309.3, b = 1619.8, c = 2410.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 155.1 and 143.1 pm via the μ₂-N atoms of the NPEt₃ groups. [B₂Cl₂(NPⁱPr₃)₃]⁺BCl₄^? · CH₂Cl₂: Space group Pna2, Z = 4, R = 0.033 for reflections with I > 2σ(I). Lattice dimensions at ?70°C: a = 1976.5, b = 860.2, c = 2612.7 pm. Within the cations the boron atoms are linked to planar, asymmetrical B₂N₂ four-membered rings with B? N distances of 153.7 and 150.5 pm via the μ₂-N atoms of two of the NPⁱPr₃ groups. The third NPⁱPr₃ group is terminally connected to the sp²-hybridized boron atom with a B? N distance of 133.5 pm and with a B? N? P bond angle of 165.3°.     

Etude des composés d'addition des acides de Lewis - XXXV. Note sur les composés d'addition entre amides et,respectivement, PdCl2 et PtCl2

The adducts of dimethylformamide, diethylformamide, dimethylacetamide and diethylacetamide with PdCl₂ and PtCl₂ have been prepared and the IR. spectra of the compounds in nujol mull or in CH₂Cl · CH₂Cl solution are studied. The lowering of the carbonyl frequency (amide I) shows that the metal is linked by a dative bond to the amide oxygen atom acting as a donor; the lowering is about 33 to 59 cm^?1. The decrease of the frequency of the carbonyl group vibration, observed in these cases as for other addition compounds of Lewis acids, is due to an intramolecular electronic displacement in the direction of the amid oxygen atom.     

Vibrational spectra and normal coordinate analysis of germylazide-do and -d3

The infrared spectra (4000–20 cm^?1) of gaseous and solid GeH₃NNN and GeD₃NNN and the Raman spectra (3000–0 cm^?1) of liquid and solid GeH₃NNN and GeD₃NNN have been recorded. The vibrational spectrum has been assigned on the basis of C_s symmetry. The GeNN bend was observed in the Raman spectrum of the gas at ~150 cm^?1; however, the frequency of the GeH₃ torsion could not be determined. A normal coordinate calculation has been carried out by utilizing a modified valence force field. The GeN stretching force constant was found to have a significantly smaller value than the corresponding force constant in GeH₃NCO and GeH₃NCS. A considerable amount of mixing was found between the GeN stretch and the NNN in-plane bend. The frequencies of the normal modes and the normal coordinate analysis of GeH₃NNN are discussed in view of the recent results reported for GeH₃NCO and GeH₃NCS.     

Theoretical studies on Lewis acidity scale and bonding character of boron trihalides BX3(X=F,C1, Br,I) by DV-Xα quantum chemical approach

The Lewis acidity scale of boron trihalides BX₃ (X=F, C1, Br, I) and character of the boron-halogen bonds have been studied by means of DV-X_m approach. Present results show that the acid strength of boron trihalides increases in the order BF₃<BCl₃<BBr₃<BI₃, in excellent agreement with experiments. Based on boron-halogen bonding character, the valence of boron atom in boron compounds can be considered M equal to five instead of three which seems to be more reasonable.     

CO2 tea laser-induced photochemical enrichment of boron isotopes

Mixtures of BCl₃ and H₂S are irradiated with 10.55 μm radiation (P(16) line of the 001–100 band of CO₂) from a TEA laser. After several hours of irradiation it is found that the maximum ¹⁰B to ¹¹B ratio of recovered gaseous boron containing material (primarily unreacted BCl₃) is 0.413 ± 0.004. The corresponding ratio of the BCl₃ starting material is 0.242 ± 0.002. The ¹⁰B concentration has therefore been increased from 19.5% to 29.2%. Further, by irradiating similar mixtures with 10.18 μm radiation (R(30) line of the same CO₂ vibrational band) this ratio changes to 0.169 ± 0.002, the ¹⁰B concentration being lowered to 14.4%. All experiments are performed in a small static system and chemical procedures for recovering milligram quantities of BCl₃ selectively enriched in either isotope are described.     

Détermination du champ de force de valence et des modes normaux de vibration des composés d'addition de l'acétone avec le trifluorure de bore

A valence force field for coordination compounds between acetone and boron trifluoride is computed: it is based upon vibrational spectra of six isotopic species and compared with the force field of free acetone and BF^?₄ ion. The formation of complex modifies the electronic state of the base and consequently the diagonal force constant of the CCO group and of the CH bonds. The force constant of the coordination bond (OB) is estimated as 2.10 mdyne Å^?1. Below 800 cm^?1 all modes involve motions of the acid and base; none corresponds to a stretching of the coordination bond.     

Rate coefficients for CS reactions with O2, O3 and NO2 AT 298 K

CS radicals have been produced by photodissociation of CS₂ at 193 nm and their disappearance monitored by LIF. The vibrationally excited CS radicals rapidly relax to CS(ν = 0). At 298 K, the rate coefficients for CS(ν = 0) reactions with O₂, O₃ and NO₂ are (2.9 ± 0.4) × 10_?19, (3.0 ± 0.4) × 10^?16 and (7.6 ± 1.1) × 10^?17 cm³ molecule^?1 s^?1 respectively. The quenching of CS(A ¹II)_ν=0 by He has a rate coefficient of (1.3 ± 0.2) × 10^?12 cm³ molecule^?1 s^?1.     

Organometallic compounds of transition metals containing phosphine and perchloroaryl ligands I. Preparation and studies of compounds of the type [MX(C6Cl5)(PPh3)2] (M  Ni,Pd)

Several stable new compounds of transition metals with C₆Cl₅ as ligand, of the type [MX(C₆Cl₅)(PPh₃)₂] (M  Pd and X  Cl, Br, I, NCS, NCO, N₃; M  Ni and X  NCS, NCO, N₃) are described. Their preparation in some cases required in situ reaction of [MX₂(PPh₃)₂], Mg and C₆Cl₆. The action of gaseous HCl and Cl₂ on the solutions of these compounds has been examined. The IR spectra of the cyanato and thiocyanato complexes indicates coordination through the nitrogen atom.     

Hexahalodiborate Dianions: A New Family of Binary Boron Halides

The electron‐precise binary boron subhalide species [B₂X₆]^2? X=F, Br, I) were synthesized and their structures confirmed by X‐ray crystallography. The existence of the previously claimed [B₂Cl₆]^2?, which had been questioned, was also confirmed by X‐ray crystallography. The dianions are isoelectronic to hexahaloethanes, are subhalide analogues of the well‐known tetrahaloborate anions (BX₄^?), and are rare examples of molecular electron‐precise binary boron species beyond B₂X₄, BX₃, and [BX₄]^?.     

Neutron inelastic scattering spectra of strongly hydrogen bonded acid oxalates NaHC2O4, KHC2O4 and LiHC2O4

Neutron inelastic scattering spectra of NaHC₂O₄, KHC₂O₄ crystals at 80 K have been recorded in the 2200-200 cm^?1 range. The lithium acid salt was also studied at different temperatures. NIS spectra are compared to the corresponding infrared and Raman spectra and an assignment is proposed. Two strong bands near 1500 and 1100 cm^?1 are assigned to δ(OH) and γ(OH) vibrations, respectively, while five weak bands below 900 cm^?1 are associated with skeletal modes, mainly bending vibrations. The OH stretching vibration is not observed and is believed to be hidden by other bands; the peak intensity must be low because of its band width which is of the order of a few hundreds wavenumbers.     

Kristallstrukturen,Normalkoordinatenanalysen und 15N‐NMRund 77Se‐NMR‐Verschiebungen von trans‐[OsO2(NCO)4]2–, trans‐[OsO2(NCS)4]2– und trans‐[OsO2(SeCN)4]2–

Crystal Structures, Normal Coordinate Analyses, and ¹⁵N NMR and ⁷⁷Se NMR Chemical Shifts of trans ‐[OsO₂(NCO)₄]^2–, trans ‐[OsO₂(NCS)₄]^2–, and trans ‐[OsO₂(SeCN)₄]^2– The crystal structures of trans‐(Ph₃PNPPh₃)₂[OsO₂(NCO)₄] ( 1 ) (orthorhombic, space group Pbca, a = 19.278(3), b = 16.674(4), c = 19.982(2) Å, Z = 4), trans(n‐Bu₄N)₂[OsO₂(NCS)₄] ( 2 ) (triclinic, space group P1, a = 12.728(3), b = 12.953(3), c = 16.255(6) Å, α = 97.39(4), β = 105.62(2), γ = 95.25(3)°, Z = 2) and trans‐(n‐Bu₄N)₂[OsO₂(SeCN)₄] ( 3 ) (tetragonal, space group I4/m, a = 13.406(2), c = 12.871(1) Å, Z = 2) have been determined by single‐crystal X‐ray diffraction analysis, showing the bonding of NCO and NCS via the N atom but the coordination of SeCN via the Se atom to osmium. Based on the molecular parameters of the X‐ray determinations the vibrational spectra have been assigned by normal coordinate analyses. The valence force constants are for 1 f_d(OsO) = 6.43, f_d(OsN) = 3.32, f_d(NC) = 14.50, f_d(CO) = 12.80, for 2 f_d(OsO) = 6.56, f_d(OsN) = 1.75, f_d(NC) = 15.00, f_d(CS) = 5.50, and for 3 f_d(OsO) = 6.75, f_d(OsSe) = 0.99, f_d(SeC) = 3.23, f_d(CN) = 15.95 mdyn/Å. The observed NMR shifts are δ(¹⁵N) = –386.6 ( 1 ), δ(¹⁵N) = –294.7 ( 2 ) and δ(⁷⁷Se) = 108.8 ppm ( 3 ).     

Heterolysis of H2 Across a Classical Lewis Pair, 2,6‐Lutidine⋅BCl3: Synthesis,Characterization, and Mechanism

We report that 2,6‐lutidine?trichloroborane (Lut?BCl₃) reacts with H₂ in toluene, bromobenzene, dichloromethane, and Lut solvents producing the neutral hydride, Lut?BHCl₂. The mechanism was modeled with density functional theory, and energies of stationary states were calculated at the G3(MP2)B3 level of theory. Lut?BCl₃ was calculated to react with H₂ and form the ion pair, [LutH⁺][HBCl₃^?], with a barrier of ΔH^≠=24.7 kcal mol^?1 (ΔG^≠=29.8 kcal mol^?1). Metathesis with a second molecule of Lut?BCl₃ produced Lut?BHCl₂ and [LutH⁺][BCl₄^?]. The overall reaction is exothermic by 6.0 kcal mol^?1 (Δ_rG°=?1.1). Alternate pathways were explored involving the borenium cation (LutBCl₂⁺) and the four‐membered boracycle [(CH₂{NC₅H₃Me})BCl₂]. Barriers for addition of H₂ across the Lut/LutBCl₂⁺ pair and the boracycle B?C bond are substantially higher (ΔG^≠=42.1 and 49.4 kcal mol^?1, respectively), such that these pathways are excluded. The barrier for addition of H₂ to the boracycle B?N bond is comparable (ΔH^≠=28.5 and ΔG^≠=32 kcal mol^?1). Conversion of the intermediate 2‐(BHCl₂CH₂)‐6‐Me(C₅H₃NH) to Lut?BHCl₂ may occur by intermolecular steps involving proton/hydride transfers to Lut/BCl₃. Intramolecular protodeboronation, which could form Lut?BHCl₂ directly, is prohibited by a high barrier (ΔH^≠=52, ΔG^≠=51 kcal mol^?1).     

Synthesis,spectroscopic characterization and crystal and molecular structure of HRu3(OCN(CH3)2)(CO)10

Dimethylamine reacts with Ru₃(CO)₁₂ to produce the η²-hydrido-η-formamido cluster complex HRu(OCN(CH₃)₂)(CO)₁₀ (I). This formulation is consistent with spectroscopic features such as the absence of v(NH) in the infrared, the presence in the Raman of v(RuHRu) at 1400 cm^?1 (v(RuDRu) at 990 cm^?1) and indication in the ¹H NMR of diastereotopic methyl groups bonded to the nitrogen atom. Since these data could not lead to an unequivocal structure assignment a single crystal X-ray study at 115 K was undertaken. The complex crystallizes in the triclinic space group, P$\text{1}$ with cell dimensions; a 7.299(33) », b 9.5037(40) », c 13.7454(57) », α 91.876(34)°, β 96.387(34)°, γ 95.341(34)° and Z = 2. The structure was solved by a combination of Patterson and Fourier techniques and refined by full matrix least squares to a final R = 0.054 and R_ω = 0.074 for 3074 unique reflections. The three ruthenium atoms define a triangle of unequal sides with both the hydride and formamido groups bridging the longest edge; the formamido group is coordinated through the carbon and oxygen atoms. The edge of the ruthenium triangle bridged both by the hydrogen atom and the formamido group is 2.8755(15) »; the other two edges of the ruthenium triangle are observed to be 2.8319(15) and 2.8577(14) », respectively. In the formamido group the distance CO 1.287(9) » and CN 1.340(10) » reflect partial double bond charater in each bond consistent with observation of two chemically distinct methyl groups on the dinitrogen atom. The hydrogen atom bridging one edge of the ruthenium triangle is asymmetrically positioned at 1.73(9) » from the ruthenium atom bonded to the oxygen atom and 1.91(9) » from the ruthenium atom bonded to the carbon atom of the carboxamido group.     

Synthese,structure cristalline et analyse vibrationnelle de l'hexathiohypodiphosphate de lithium Li4P2S6

The crystalline compound Li₄P₂S₆ is obtained either by devitrification of Li₄P₂S₇ glass at 450°C with sulfur formation or by crystallisation at 450°C of a Li₂S, P and S melt. The structure determination has been solved by X-ray diffraction on a monocrystal. The unit cell is hexagonal $\text{P6}{}_3\text{mcm}$ with a = 6.070(4), c = 6.577(4) Å, V = 209 ų, Z = 1. Intensities were collected at 293°K with Kα (λ = 0.71069 Å) Mo radiation on an automatic Nonius CAD-4 diffractometer. The structure was solved under the assumption of random disorder of P atoms over two sites (occupancy factor of 0.5). Anisotropic least-squares refinement with W = 1 gave R = 0.047 for 90 independent reflections and 9 variables. The structure is built according to an ABAB sequence sulfur packing. Per unit cell, four out of six octahedral sites are occupied by Li ions, and the other two are statistically filled (0.5) by PP pairs. The PP central bond (2.256(13) Å) links two staggered PS₃ groups (PS = 2.032(5) Å) to form the D_3d symmetry P₂S^4?₆ anion. Infrared and Raman spectra show features very similar to those of Na₄P₂S₆, 6H₂O and M^IIPS₃ compounds. A new assignment in terms of symmetry species is proposed for the P₂S₆ internal modes, which is confirmed by a normal coordinate calculation using a valence force field; the stretching force constants f_PP and f_PS are equal to 1.6 and 2.7 mdyne Å^?1, respectively.     

Crystal structure of Fe2P2O7

Fe₂P₂O₇ crystallizes in the $\text{C}\text{1}$ space group with lattice parameters a = 6.649(2)Å, b = 8.484(2)Å, c = 4.488(1)Å, α = 90.04°, β = 103.89(3)°, γ = 92.82(3)°, and ?_cal = 3.86 g/cc. It is essentially isostructural with β-Zn₂P₂O₇. As in the Zn compound, the bridging oxygen atom in the P₂O₇ group shows a high anisotropic thermal motion. It appears that the P-O-P bond angle is linear as a result of extensive π bonding with the p orbitals on the bridging oxygen atom. The high thermal motion is vibration of the atom into cavities in the structure.     

Coordination d'anions organophosphores: 1Ère partie. Complexes du zinc(II)

Twelve compounds of the type [ZnXL], where L^?1 is the anion {(C₂H₅O)₂POCHCOCH₂NR₂}^? with R = CH₃ or C₂H₅ and X = Cl, Br, I, NCO, NCS, NCSe, have been synthesized. For eleven, the unit-cell dimensions have been reported. Chemical bonding with the central zinc atom is discussed.     

Mean amplitudes and shrinkages for SiH3NCO and SiH3NCS

Mean amplitudes and shrinkages are calculated from spectroscopic data for SiH₃NCO, SiD₃NCO, SiH₃NCS and SiD₃NCS. The lowest frequency (ν₁₀) in each of the molecules is uncertain, and its influence on the calculated amplitude parameters is investigated. The results are compared with electron diffraction studies.     

High-spin Mangan(II)-Phthalocyanine: Darstellung und spektroskopische Eigenschaften von Acidophthalocyaninatomanganat(II)

High Spin Manganese(II) Phthalocyanines: Preparation and Spectroscopical Properties of Acidophthalocyaninatomanganate(II) Acidophthalocyaninatomanaganese(III) is reduced by boranate, thioacetate or hydrogensulfide to yield acidophthalo-cyaninatomanganate(II) ([Mn(X)Pc^2?]^?; X = Cl, Br, NCO, NCS) being isolated as tetra(n-butyl)ammonium salt. In the cyclovoltammogram of [Mn(NCO)Pc^2?]^? the halv-wave potential for the redoxcouple Mn^II/Mn^III is at ?0.13 V, that of the first ring reduction at ?0.99 V. The magnetic moments are indicative of high-spin ⁶A₁ ground states: μ_Mn = 5.84 (NCO), 5.78(Cl), 5.65 (Br), 5.68 μ_B (NCS). A Curie-like temperature dependence of μ_Mn is observed in the region 300–30 K. Below 30 K an increase in μ_Mn occurs due to weak intermolecular ferromagnetic coupling. The ESR spectra confirm the S = 5/2 ground state with a strong g = 6 resonance observed (A_Mn = 80 G) as expected for an axially distorted ligand-field. Besides the typical π-π* transitions of the Pc^2?-ligand several weak bands are observed in the Uv-vis-n.i.r. spectra at ca. 7.5, 9.1, 14.0 and 19.0 kK that are assigned to trip-multiplet transitions. In resonance with the band at 19.0 kK the Mn? X stretching vibration (v(MnX)) is resonance Raman enhanced: X = NCO: 319, Cl: 286, SCN: 238, Br: 202 cm^?1. These vibrational frequencies are confirmed by the f.i.r. spectra. In the case of the thiocyanato-complex probably both forms of bonding of the ambident NCS-ligand are present (v(Mn? NCS): 274 cm^?1). The frequencies of the vibrations of the inner (CN)₈ ring are reduced by up to 20 cm^?1 as compared with those of low spin Mn^II phthalocyanines.