The Synthesis of the Arene Clusters Ru6C(CO)14(η6-Arene) (Arene = C6H5CHMe2, C6H5C4H9, C6H5C3H7, and C6H5C3H5)

On reaction with Ru₃(CO)₁₂, isopropenylbenzene and 4-phenyl-l-butene undergo hydrogenation, to yield the clusters, Ru₆C(CO)₁₄(⁶-C₆H₅CHMe₂) 1 and Ru₆C(CO)₁₄(⁶-C₆H₅C₄H₉) 2, respectively. With allylbenzene, both hydrogenation and isomerization occurs affording Ru₆C(CO)₁₄(⁶-C₆H₅C₃H₇) 3 and Ru₆C(CO)14(⁶-C₆H₅C₃H₅) 4. The structures of 1 and 2 have been established by single crystal X-ray diffraction. One of the Ru–Ru bond lengths in 2 is unusually long and extended Hückel molecular orbital calculations have been used in an attempt to rationalize this feature.     

Heats of formation of C(6)H(5)(•), C(6)H(5)(+), and C(6)H(5)NO by threshold photoelectron photoion coincidence and active thermochemical tables analysis

Threshold photoelectron photoion coincidence has been used to prepare selected internal energy distributions of nitrosobenzene ions [C(6)H(5)NO(+)]. Dissociation to C(6)H(5)(+) + NO products was measured over a range of internal energies and rate constants from 10(3) to 10(7) s(-1) and fitted with the statistical theory of unimolecular decay. A 0 K dissociative photoionization onset energy of 10.607 ± 0.020 eV was derived by using the simplified statistical adiabatic channel model. The thermochemical network of Active Thermochemical Tables (ATcT) was expanded to include phenyl and phenylium, as well as nitrosobenzene. The current ATcT heats of formation of these three species at 0 K (298.15 K) are 350.6 (337.3) ± 0.6, 1148.7 (1136.8) ± 1.0, and 215.6 (198.6) ± 1.5 kJ mol(-1), respectively. The resulting adiabatic ionization energy of phenyl is 8.272 ± 0.010 eV. The new ATcT thermochemistry for phenyl entails a 0 K (298.15 K) C-H bond dissociation enthalpy of benzene of 465.9 (472.1) ± 0.6 kJ mol(-1). Several related thermochemical quantities from ATcT, including the current enthalpies of formation of benzene, monohalobenzenes, and their ions, as well as interim ATcT values for the constituent atoms, are also given.     

[(C6H5 NO2)Pr(H2O)4](CrMo6O24H6)·(C6H5NO2)·2.5H2O的合成与晶体结构

用常规合成方法制备了基于Anderson结构阴离子的二维层状化合物[(C6H5NO2)2Pr(H2O)4](CrMo6O24H6)·2.5H2O,通过红外光谱和X射线单晶衍射对其进行了表征.结果表明,该化合物属于单斜晶系,C2/c空间群.a=2.3442(9)nm,b=1.3291(5)nm,c=2.458(1)nm,β=103.08(1)°,V=7.460(5)nm3,R1=0.0727,wR2=0.1903.结构分析表明,[CrMo6O24H6]3-阴离子通过端氧担载一个配位的Pr3+离子形成中性的(C6H5NO2)Pr(H2O)4(CrMo6O24H6)基团,相邻的中性基团在Ot—Pr—Ot桥联下形成一维链,链与链又通过异烟酸的桥联形成二维层状结构.     

混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构研究

本文用电化学方法和X射线单晶结构分析, 研究了混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构, 由循环伏安结果, 分别讨论了簇合物中(C5H5FeC5H4和C2O2中心的成键性质, X射线单晶结构分析表明: 晶体属单斜晶系, 空间群为P21, 晶胞参数a=11.845(6), b=8.155(6), c=24.031(6)A, β=90.88°,晶胞中分子数Z=4, 密度Do=1.637g.cm^-^2, 分析了(C5H5FeC5H4C2Ph)Co2(CO)6的结构特点, 并从成键角度讨论了(RC2R^1)Co(CO)6类簇合物的结构随RC2R^1不同而变化的规律。     

混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构研究

本文用电化学方法和X射线单晶结构分析, 研究了混合簇合物(C5H5FeC5H4C2Ph)Co2(CO)6的结构, 由循环伏安结果, 分别讨论了簇合物中(C5H5FeC5H4和C2O2中心的成键性质, X射线单晶结构分析表明: 晶体属单斜晶系, 空间群为P21, 晶胞参数a=11.845(6), b=8.155(6), c=24.031(6)A, β=90.88°,晶胞中分子数Z=4, 密度Do=1.637g.cm^-^2, 分析了(C5H5FeC5H4C2Ph)Co2(CO)6的结构特点, 并从成键角度讨论了(RC2R^1)Co(CO)6类簇合物的结构随RC2R^1不同而变化的规律。     

Substitution and insertion reactions of (η5-C5H5)Cr(CO)3C2H5

The complex (η⁵-C₅H₅)Cr(CO)₃Cp42 H₅ has been made and its reactions with σ donor ligands L (L = (MeO)₃P and (EtO)₃P) and with SO₂ studied. The alkyl phosphites give compounds of the composition (η⁵-C₅H₅)Cr(CO)₂LC₂H₅, and sulfur dioxide gives the corresponding S-sulfinato (η⁵-C₅H₅)Cr(CO)₃SO₂C₂H₅.     

双核钴簇合物(C6H5C2R)Co2(CO)6的合成

羰基钴簇合物Co₂(CO)₈可用于有机合成的催化剂。但Co₂(CO)₈本身不稳定,易被氧化。因此,研究不向CO₂簇合物的稳定性及其催化性能具有一定的意义。     

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) ?, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) ?(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) ?, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) ?(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not significantly couple with the S = 1/2 vanadyl groups. The susceptibility data can be successfully reproduced assuming a distorted ligand field for the Co(2+) ions (1) and an O(h)-symmetric Ni(2+) ligand field (2).     

Why are [P(C6H5)4](+)N3- and [As(C6H5)4](+)N3- ionic salts and Sb(C6H5)4N3 and Bi(C6H5)4N3 covalent solids? A theoretical study provides an unexpected answer

A recent crystallographic study has shown that, in the solid state, P(C(6)H(5))(4)N(3) and As(C(6)H(5))(4)N(3) have ionic [M(C(6)H(5))(4)](+)N(3)(-)-type structures, whereas Sb(C(6)H(5))(4)N(3) exists as a pentacoordinated covalent solid. Using the results from density functional theory, lattice energy (VBT) calculations, sublimation energy estimates, and Born-Fajans-Haber cycles, it is shown that the maximum coordination numbers of the central atom M, the lattice energies of the ionic solids, and the sublimation energies of the covalent solids have no or little influence on the nature of the solids. Unexpectedly, the main factor determining whether the covalent or ionic structures are energetically favored is the first ionization potential of [M(C(6)H(5))(4)]. The calculations show that at ambient temperature the ionic structure is favored for P(C(6)H(5))(4)N(3) and the covalent structures are favored for Sb(C(6)H(5))(4)N(3) and Bi(C(6)H(5))(4)N(3), while As(C(6)H(5))(4)N(3) presents a borderline case.     

An infrared and Raman spectroscopic study of Td-type 4,4′-bipyridylcadmium(II) tetracyanometallate (II) benzene (1/2) clathrates: Cd(C10H8N2)Cd(CN)4 · 2C6H6 and Cd(C10H8N2)Hg(CN)4 · 2C6H6

Two new benzene clathrates of the form Cd(4,4-bipyridyl)M(CN)₄ · 2C₆H₆, (M=Cd or Hg) have been prepared in powder form. Their spectral data were compared with those of the corresponding host complexes and found to be consistent with the host structure found in Td-type clathrates.     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Crystal and molecular structure of the [Nd2(H2O)8(C6F5COO)6]·2H2O Compound

A compound with the composition Nd(C₆F₅COO)₃· H₂O (I) is prepared. Single crystals are grown, and their single crystal XRD analysis of the Nd₂(H₂O)₈(C₆F₅COO)₆]·2H₂O (II) compound is performed. The crystals are triclinic: a = 7.693(2) Å, b = 9.394(2) Å, c = 18.203(4) Å, α = 81.91(3)°, β = 84.41(3)°, γ = 88.97(3)°, Z = 1, d _x = 2.223 g/cm³. The structure is composed of symmetrical molecules of the binuclear [Nd₂(H₂O)₈(C₆F₅COO)₆] complex and crystallization water molecules. The C₆F₅COO^- ligands are monodentate and tridentate bridging- chelating, which results in a closure of two four-membered chelate cycles NdO₂C and a four-membered metal cycle Nd₂O₂. The NdO₉ polyhedron is a distorted one-capped tetragonal antiprism.     

Molecular structure of two dicyclopentadienylmolybdenum derivatives containing a four-membered ring [Mo(η5-C5H5)2(2-NHNC5H4)][PF6] and [Mo(η5C5H5)2(2-ONC5H4)][PF6]

The structure of the new compound [Mo(η⁵-C₅H₅)₂(2-NHNC₅H₄)][PF₆] (1) has been determined. The crystals are orthorhombic, space group Pca2₁ with a 20.807(1), b 8.0030(8), c 10.056(3) Å, V 1674.5 ų, Z = 4. The structure of [Mo(η⁵-C₅H₅)₂(2-ONC₅H₄)][PF₆] (2) has also been determined. The crystals are orthorhombic, space group Pnma with a 12.727(3), b 10.174(2), c 12.918(1) Å, V 1672.8 ų, Z = 4. The structures were solved by Patterson and difference electron density syntheses and refined by least-squares to R of 0.028 for 1287 reflections for 1 and 0.059 for 1178 reflections for 2.Although not isostructural the two cationic complexes have equivalent geometries with the normal bent bismetallocene structure. For 1 the MoN bond lengths are 2.160(8) and 2.142(9) Å, with a NMoN bond angle of 59.8(3)°, whereas for 2 MoO is 2.142(10), MoN is 2.138(11) Å, the NMoO angle is 61.2(4)°. These parameters are discussed and compared with the corresponding data for similar biscyclopentadienyl complexes of molybdenum(IV). Extended Hückel molecular orbital calculations have been carried out to throw light on the nature of the bonding between the metal and the bidentate ligand.     

Reactions of trans-[Pt(H2){P(C6H11)3}2] with heterocumulenes. The crystal and molecular structure of trans-[Pt{P(C6H11)3}2(H){OCHC(C6H5)2}]

Trans-PtH₂(PCy₃)₂ (1) reacts with phenylisocyanate (2) and with diphenylketene (3) to yield the formamido complex (4) and the vinyloxo complex (5), respectively. The structure of 5 has been determined by X-ray diffraction.     

Triethylaluminum-Based Ferrocenylalanes. Synthesis and Crystal Structure of (η5−C5H5)Fe[η5−C5H4Al2(C2H5)4Cl]

Abstract

The trietheylaluminum based ferrocenylalane (η⁵?C₅H₅)Fe[η⁵?C₅H₄Al₂(C₂H₅)₄Cl] was prepared from the reaction of triethylaluminum with chloromercuriferrocene in toluene and characterized by single crystal X-ray diffraction. The compound crystallizes in the triclinic space group P 1 with unit cell dimensions a = 9.353(3) Å, b = 10.281(7) Å, c = 11.599(9) Å, α = 79.64(7)°, β = 69.41(6)°, γ = 84.33(4)°, and Z = 2 for D_c = 1.27 g cm^?3. Full-matrix least-squares refinement has led to a final R factor of 0.068 based on 1866 independent observed reflections. The two diethylaluminum units are bridged by a chlorine atom and one carbon atom of a cyclopentadienyl group, thus forming an Al-Cl-Al-C ring. The four-membered ring is planar to within 0.02 Å. The Al-Cl distances are 2.404(4) Å and 2.266(5) Å. The Al-Cl-Al angle is 78.9(1)° while the Al-C-Al angle is 91.3(4)°. No significant aluminum-iron interaction is observed (Al… Fe = 3.137(4) Å).     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

Synthesis and structure of the organoantimony peroxide solvates [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·1.5C4H8O2 and [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·6C4H8O2

The organoantimony peroxide (Ar₂SbO)₄(O₂)₂ (Ar = C₆H₃OMe-2, Br-5) was synthesized by the oxidation of Ar3Sb with hydrogen peroxide in the presence or acetoxime or acetophenone oxime in dioxane. The product crystallizes with various content of the solvent molecules in the crystal unit cell [1.5 (I) and 6 (II), respectively]. An X-ray diffraction analysis of the solvates was performed. Four antimony atoms in the peroxide are in the octahedral coordination, and are linked through bridging oxygen atoms and two peroxide groups. The distances Sb-C, Sb-O_bridge, Sb-O_peroxide, O-O and Sb...Sb are 2.117–2.122, 1.960–1.972, 2.193–2.235, 1.461, 1.465 and 3.223–3.237 Å in I, and 2.112, 2.119, 1.957, 1,966, 2.204, 2,246, 1,467, and 3.2439 Å in II.     

Infrared investigations of the order–disorder ferroelectric phase transitions in imidazolium halogenobismuthates(III) and halogenoantimonates(III): (C3N2H5)5Bi2Cl11, (C3N2H5)5Bi2Br11 and (C3N2H5)5Sb2Br11

Infrared spectra of the powdered (C₃N₂H₅)₅Bi₂Cl₁₁, (C₃N₂H₅)₅Bi₂Br₁₁and (C₃N₂H₅)₅Sb₂Br₁₁ crystals in the region of internal vibrations of the imidazolium cations (3600 and 400 cm⁻¹) at the temperature intervals of 10–300 K, covering paraelectric–ferroelectric phase transitions, are presented and discussed in this paper. The research shows that the vibrational states of the imidazolium cations change markedly during the paraelectric–ferroelectric phase transition. The continuous nature of these transitions is well reflected in the infrared spectra, which is consistent with the previous X-ray and dielectric findings.     

Oxidation of theexo- andendo-phenylcyclohexadienyl iron complexes Fe(η5-6-PhC6H6) (η5- C5H5)

The roe of oxidatively induced homolyhc scission a the C(sp³)-H bonds in the iron phenykychhexadienyl complexes Fe(⁵-6-PhC₆H₆)(⁵-C₅H₅) (1) depends on the spatial orientation of the Ph substitutent. In the case of the (1 _endo ⁺) radical cation this process, resulting in the cationic biphenyl complex (Fe(⁶ -C₆H₅C₆H₅)(⁵-C₅H₅)]⁺ (2 ⁺), is fast and proceeds for several minutes. In the case of the more stable radical cation (1 _exo ⁺) the formation of 2⁺ is slow and takes tens minutes to complete.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1698–1700, July, 1996.     

Tantalocene complexes as bidentate métalloligands: (C5Me5)(C5H4X)Ta(H2)(PPh2) (C5Me5) (C5H4X)Ta(CO) (PPh2) (X = PPh2, CH2CH2NMe2)

The synthesis of new bidentate métalloligands derived from tantalocene(C₅Me₅)(C₅H₄X)Ta(H₂)(PPh₂) (X = PPh₂, 2P; X = CH₂CH₂NMe₂2N) and (C₅Me₅)(C₅H₄X)Ta(CO)(PPh₂) 4(P,N) is described. When opposed to chromium unsaturated fragments the phosphino functionalised complexes 2P and 4P act as chelating bidentate ligands affording Ta(V) (C₅Me₅)(C₅H₄PPh₂)Ta(CH₂) (μ-PPh₂)Cr(CO)₄ or Ta(III) (C₅Me₅)(C₅H₄PPh₂)Ta(CO)(μ-PPh₂)Cr(CO)₄ bimetallic complexes. The same reaction carried out starting from 2N gives rise to a μ-phosphido, μ-hydrido dibridged complex Cp*(C₅H₄CH₂CH₂NMe₂)TaH(μ-H)(μ-PPh₂)Cr(CO)₄.