One-pot synthesis of the new dianionic ligand [Na]2[C5H4CO2(CH2)2NTs]; preparation and structures of two rhodium derivatives

The new dianionic ligand [Na]₂[C₅H₄CO₂(CH₂)₂NTs] (1) having an alkoxycarbonyl and an amide group in the same side chain has been prepared by a single step, high yield procedure. The synthesis of the related rhodium complexes [Rh{η⁵-C₅H₄CO₂(CH₂)₂N(H)Ts}(NBD)] (3) and [Rh{η⁵-C₅H₄CO₂ (CH₂)₂N(Me)Ts}(NBD)] (4) is reported as well as their X-ray molecular structures.     

Synthesis, molecular structure, and catalytic activity of borohydride complexes [(Me3Si)2NC(NPri)2]2Nd(BH4)2Li(thf)2 and [(Me3Si)2NC(NPri)2]2Sm(BH4)2Li(thf)2

The reactions of lanthanide tris(borohydrides) Ln(BH₄)₃(thf)₃ (Ln = Sm or Nd) with 2 equiv. of lithium N,N′-diisopropyl-N′-bis(trimethylsilyl)guanidinate in toluene produced the [(Me₃Si)₂NC(NPrⁱ)₂]Ln(BH₄)₂Li(thf)₂ complexes (Ln = Sm or Nd), which were isolated in 57 and 42% yields, respectively, by recrystallization from hexane. X-ray diffraction experiments and NMR and IR spectroscopic studies demonstrated that the reactions afford monomeric ate complexes, in which the lanthanide and lithium atoms are linked to each other by two bridging borohydride groups. The complexes exhibit catalytic activity in polymerization of methyl methacrylate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–445, March, 2007.     

Synthesis, structure and magnetic behavior of a new three-dimensional Manganese phosphite-oxalate: [C2N2H10][Mn2(OH2)2(HPO3)2(C2O4)]

A novel manganese phosphite-oxalate, [C₂N₂H₁₀][Mn₂^II(OH₂)₂(HPO₃)₂(C₂O₄)] has been hydothermally synthesized and its structure determined by single-crystal X-ray diffraction. The structure consists of neutral manganese phosphite layers, [Mn(HPO₃)]_∞, formed by MnO₆ octahedra and HPO₃ units, cross-linked by the oxalate moieties. The organic cations occupy the middle of the 8-membered one-dimensional channels. Magnetic studies indicate weak antiferromagnetic interactions between the Mn²⁺ ions.     

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).     

X-ray crystal structures and solution dynamics of sodium organofluorotitanates [Na{Ti2(C5Me5)2F7}] and [NaTi6(C5Me5)5F20(H2O)]·(THF)

[Na{Ti₂(C₅Me₅)₂F₇}] (1) was prepared from sodium fluoride and [{Ti(C₅Me₅)F₃}₂] [H.W. Roesky, et al., Angew. Chem. Int. Ed. Engl. 31 (1992) 864-866]. The solid-state 1 consists of a polymeric chain of two rows of dititanate anions [Ti₂(C₅Me₅)₂F₇]⁻ connected by sodium ions in the middle of the chain. Each sodium ion is coordinated by five fluorine atoms from three [Ti₂(C₅Me₅)₂F₇]⁻ anions. The variable-temperature ¹⁹F NMR of CD₃CN solution of 1 revealed interconversions of monomeric species [Na(CD₃CN)_n{Ti₂(C₅Me₅)₂F₇}] (1solv) with different number of CD₃CN ligands on the sodium ion. The addition of HMPA to the CD₃CN solution of 1 allows ¹⁹F NMR observation of 1·HMPA (1a) and 1·HMPA·CD₃CN (1b) in the slow exchange. The solid-state structure of [NaTi₆(C₅Me₅)₅F₂₀(H₂O)]·(THF) (2·THF) reveals the sodium ion coordinated by four fluorine atoms from the anion [Ti₂(C₅Me₅)₂F₇]⁻ and by three fluorine atoms from the cluster [Ti₄(C₅Me₅)₃F₁₃(H₂O)].     

Synthesis of trinuclear silicon-, germanium-, and tin-containing tungsten carbene complexes [(ButO)2(Cl)2W=CH]2EPh2 (E = Si, Ge, or Sn). Crystal structure of [(ButO)2(Cl)2W=CH]2SiPh2 complex

New trinuclear organosilicon, organogermanium, and organotin-containing tungsten carbene complexes Ph₂E[CH=WCl₂(OBu^t)₂]₂ (E = Si, Ge, or Sn) were synthesized by the reaction of the trinuclear carbyne complexes Ph₂E[C≡W(OBu^t)₃]₂ with HCl. The tin-containing carbene complex is thermally unstable and was identified in solution by ¹H and ¹³C NMR spectroscopy. The silicon-and germanium-tungsten carbene complexes were isolated in high yields as individual crystals and were characterized by elemental analysis, IR spectroscopy, and ¹H and ¹³C NMR spectroscopy. The structure of the silicon-containing complex Ph₂Si[CH=WCl₂(OBu^t)₂]₂ was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2424–2427, November, 2005.     

In[NC5H3(CO2)2](OH2)F: A new layered indium-organic framework material (NC5H3(CO2)2=2,6-pyridinedicarboxylate)

A new layered indium-organic framework material, In[NC₅H₃(CO₂)₂](OH₂)F has been synthesized by a hydrothermal reaction using In₂O₃, NH₄F, 2,6-NC₅H₃(CO₂H)₂ (2,6-pyridinedicarboxylic acid), HF, and water at 200 °C. Single-crystal X-ray diffraction was used to determine the structure of the reported material. In[NC₅H₃(CO₂)₂](OH₂)F has a novel layered structure consisting of InO₅NF polyhedra and the pyridinedicarboxylate organic linker. Detailed structural analyses with full characterization including infrared spectrum, thermogravimetric analysis, elemental analysis, exchange reactions for the coordinated water molecule, and gas adsorption experiments are reported.     

Synthesis and structural characterization of (COT)Pr(C13H8CH2CH2OMe)(THF) containing the chelating 9-(2-methoxyethyl)fluorenyl ligand

Treatment of 9-(2-methoxyethyl)fluorene, C₁₃H₉CH₂CH₂OMe (1), with potassium hydride in THF/toluene in the presence of 18-crown-6 afforded orange-red crystalline K(18-crown-6)C₁₃H₈CH₂CH₂OMe (2) in 59% yield. A “constrained geometry”-type praseodymium complex containing the 9-(2-methoxyethyl)fluorenyl ligand, (COT)Pr(C₁₃H₈CH₂CH₂OMe)(THF) (3), was prepared by treatment of dimeric [(COT)Pr(μ-Cl)(THF)₂]₂ (COT = η⁸-cyclooctatetraenyl) with in situ prepared KC₁₃H₈CH₂CH₂OMe. The molecular structures of 1, 2, and 3 were determined by single-crystal X-ray diffraction.     

Alkynethiolate ligands in the syntheses of iron carbonyl derivatives. Crystal structure of [(η-C5H5)Fe(CO)2(SCCSiMe3)]

The complexes [(η⁵-C₅H₅)Fe(CO)₂(SCCR)] (R=^tBu, SiMe₃) have been obtained by reaction of [(η⁵-C₅H₅)Fe(CO)₂I] and the corresponding LiSCCR. These are the first examples of mononuclear iron compounds containing alkynethiolate ligands. The crystal structure of [(η⁵-C₅H₅)Fe(CO)₂(SCCSiMe₃)] has been determined by X-ray diffraction. The role of [(η⁵-C₅H₅)Fe(CO)₂(SCCSiMe₃)] as a metalloligand in its reactions with metal carbonyls has been explored.     

Synthesis, characterization, and X-ray crystal structure of the octabromodiosmate(III) salt [(C5Me4H)2OsBr]2[Os2Br8] and its conversion to [(C5Me4H)2OsBr][Os2HBr4(cod)2]

Treatment of hexabromoosmic acid, H₂OsBr₆, with 4 equiv. of tetramethylcyclopentadiene (C₅Me₄H₂) in tert-butanol at reflux for 8 h affords the unusual salt [(C₅Me₄H)₂OsBr]₂[Os₂Br₈], 1, which is the bis(tetramethylcyclopentadienyl)bromoosmocinium(IV) salt of the octabromodiosmate(III) dianion. The brown color of the salt suggests that the anion adopts an eclipsed conformation (D_4h symmetry) and this conclusion has been confirmed by a single-crystal X-ray diffraction experiment. The X-ray crystal structure indicates that the osmium atoms in the anion are disordered over two sites. The bromine atoms show no evidence of disorder and are disposed in a quasi-cubic arrangement; the two Os-Os vectors are almost exactly orthogonal to each other and each vector points toward a different pair of opposite square faces of the Br₈ cube. The Os-Os bond distances are 2.219(5) and 2.229(1) Å; the average Os-Br distance in the anion is 2.417(2) Å. Treatment of [(C₅Me₄H)₂OsBr]₂[Os₂Br₈] with excess 1,5-cyclooctadiene in ethanol at gentle reflux for 3 h affords [(C₅Me₄H)₂OsBr][Os₂HBr₄(cod)₂], 2. An X-ray crystallographic study was carried out on a sample in which the cation was a mixture of [(C₅Me₄H)₂OsBr⁺] and [(C₅Me₄H)₂OsH⁺]. The results demonstrate that the anion adopts a confacial bioctahedral structure in which the hydride ligand and two bromides bridge between the two osmium centers. The CC bonds of the cod ligands are trans to the bridging bromide groups. The Os-Os bond distance in the anion is 2.874(1) Å. The average Os-Br distance is 2.596(2) Å for the bridging bromides and 2.565(2) Å for the terminal bromides. Compound 2 is the first example of an anionic diosmium complex containing a bridging hydride. The reaction of 1 with cod also results in the formation of bis(tetramethylcyclopentadienyl)osmocene, (C₅Me₄H)₂Os, 3, which has been isolated and characterized. Treatment of (C₅Me₄H)₂Os with 1.0 equiv. of HBF₄ · Et₂O affords the osmocinium salt [(C₅Me₄H)₂OsH][BF₄].     

A new uranyl niobate sheet in the cesium uranyl niobate Cs9[(UO2)8O4(NbO5)(Nb2O8)2]

A new cesium uranyl niobate, Cs₉[(UO₂)₈O₄(NbO₅)(Nb₂O₈)₂] or Cs₉U₈Nb₅O₄₁ has been synthesized by high-temperature solid-state reaction, using a mixture of U₃O₈, Cs₂CO₃ and Nb₂O₅. Single crystals were obtained by incongruent melting of a starting mixture with metallic ratio=Cs/U/Nb=1/1/1. The crystal structure of the title compound was determined from single crystal X-ray diffraction data, and solved in the monoclinic system with the following crystallographic data: a=16.729(2) Å, b=14.933(2) Å, c=20.155(2) Å β=110.59(1)°, P2₁/c space group and Z=4. The crystal structure was refined to agreement factors R₁=0.049 and wR₂=0.089, calculated for 4660 unique observed reflections with I?2σ(I), collected on a BRUKER AXS diffractometer with MoKα radiation and a CCD detector.In this structure the UO₇ uranyl pentagonal bipyramids are connected by sharing edges and corners to form a uranyl layer corresponding to a new anion-sheet topology, and creating triangular, rectangular and square vacant sites. The two last sites are occupied by Nb₂O₈ entities and NbO₅ square pyramids, respectively, to form infinite uranyl niobate sheets stacking along the [010] direction. The Nb₂O₈ entities result from two edge-shared NbO₅ square pyramids. The Cs⁺ cations are localized between layers and ensured the cohesion of the structure.The cesium cation mobility between the uranyl niobate sheets was studied by electrical measurements. The conductivity obeys the Arrhenius law in all the studied temperature domains. The observed low conductivity values with high activation energy may be explained by the strong connection of the Cs⁺ cations to the infinite uranyl niobate layers and by the high density of these cations in the interlayer space without vacant site.Infrared spectroscopy investigated at room temperature in the frequency range 400-4000 cm⁻¹, showed some characteristic bands of uranyl ion and niobium polyhedra.     

Regioselectivity of reactions of vinyl- and isopropenylcyclopentadienide anions with electrophilic agents. Synthesis and crystal structures of complexes [C5H4C(Me)=CH2]ZrCl3 · 2THF and [C5Me4CH=CH2]ZrCl3 · 2THF

Regioselectivity of the reactions of lithium vinyl- and isopropenylcyclopentadienides C₅H₄C(R)=CH₂ ^-Li⁺(R = H, Me) and lithium tetramethylvinylcyclopentadienide C₅Me₄CH=CH₂ ^-Li⁺ with various electrophilic agents (Me₃SiCl, Me₃SnCl, Et₂PCl, 2-chloro-1, 3-dioxaphospholane, and MeI) was studied. Two new monocyclopentadienyl zirconium complexes, [C₅H₄C(Me) = CH₂]ZrCl₃ · 2THF and [C₅Me₄CH=CH₂]ZrCl₃ · 2THF, were synthesized. Their crystal structures were established by X-ray diffraction. The results of quantum chemical calculations for the C₅H₄C(R) = CH₂ ^- (R = H, Me) and C₅Me₄CH=CH₂ ^- anions by the DFT method (RMPW1PW91) with the 6-311+G(d, p) split valence basis set are in good agreement with experimental data on the regioselectivity of their reactions with electrophilic agents.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 390–399, February, 2005.     

Synthesis and structure of the iron-substituted silylacetylene [(η-C5H5)Fe(CO)2SiMe2C]2 and its cobalt hexacarbonyl derivative [(η-C5H5)Fe(CO)2SiMe2C]2 · Co2(CO)6

A transition metal-substituted silylacetylene [(η⁵-C₅H₅)Fe(CO)₂SiMe₂C]₂, [FpMe₂SiC]₂ (I) was synthesized and characterized spectroscopically and structurally. I crystallized in the monoclinic space group P2₁/n, A = 13.011(3) Å B = 12.912(3) Å, C = 13.175(5) Å, β = 94.95(2). The acetylene linkage is reactive toward Co₂(CO)₈ to form I. Co₂(CO)₆ (II) which was also characterized spectroscopically and by single crystal X-ray diffraction. II crystallized in the orthorhombic space group Pbca, A = 17.64(2) Å, B = 14.225(10) Å, C = 24.49(2) Å.     

Two-electron reductive reactivity of trivalent uranium tetraphenylborate complexes of (C5Me5) and (C5Me4H)

The reductive reactivity of the (BPh₄)¹⁻ ligand in pentamethylcyclopentadienyl [(C₅Me₅)₂U][(μ-η²:η¹-Ph)₂BPh₂] (1) was compared with that of the tetramethyl analog, [(C₅Me₄H)₂U][(μ-η⁶:η¹-Ph)(μ-η¹:η¹-Ph)BPh₂] (2) using PhSSPh as a probe to determine if the mode of (BPh₄)¹⁻ bonding affected the reduction. Both complexes act as two-electron reductants to form (C₅Me₄R)₂U(SPh)₂ [R = Me, 3; H, 4], but only in the R = H case could the product be crystallographically characterized. An improved synthesis of 1 from [(C₅Me₅)₂UH]₂ (5) and [Et₃NH][BPh₄] is also reported as well as its reaction with MeCN that provides another route to the unusual, parallel-ring, uranium metallocene [(C₅Me₅)₂U(NCMe)₅][BPh₄]₂ (6).     

Rh2(μ-SC6H5)2(CO)4的合成和晶体结构

一种路易斯碱，例如膦（PR3）或异氰化物（CNR）加到双核或多核络合物中，会导致低核物种的形成，这就伴随有金属一金属键的断裂[1]．这样的例子很多，如我们曾用F33（CO）12与P（SC6H5）3反应，分离出三个不同的两核铁数合物[2]．现在我们报导另一个例子：用Rh4（CO）12与P（SC6H小反应，同样也得到一个两核物种WhZ（P－SC6H巾（C）4．该化合物首先由B0ltoll＊等人用WhZ（CO）ZC12与苯硫酚C6H。SH反应得到，但有关它的X－rar晶体结构的测定还未见报导·与之相似的化合物Rh。（p－SC。H。F）。门O）。的结构已由ClaverN…     

Diphenylbutadiene-bridged gadolinium complex [GdCl2(THF) 3]2(μ-Ph2C4H4) · 3THF: The synthesis and crystal structure

The diphenylbutadiene-bridged gadolinium complex [GdCl₂(THF)₃]₂(μ-Ph₂C₄H₄) · 3THF (1) has been obtained by the reaction of Gd(III) chloride with diphenylbutadienepotassium. The molecular structure of 1 was determined by X-ray diffraction. The complex 1 has a binuclear structure in which a bridging diphenylbutadiene ligand is η⁴-bonded to the Gd atoms connecting two GdCl₂(THF)₃ units. Both Gd atoms have a distorted octahedral environment. At the Gd atom the two Cl atoms are in trans positions and the four other coordination sites are occupied by the three O atoms of THF molecules and the η⁴-bonded C₄H₄ fragment of a diphenylbutadiene ligand. In the two η⁴-bonded GdC₄H₄ fragments one of the Gd-C η⁴-distances is significantly elongated (2.86(3) and 2.97(3) Å) compared with other three (2.65(3)–2.69(3) and 2.67(3)—2.77(3) Å). The magnetic moment of Gd, equal to 8.1 BM, is typical for Gd³⁺ compounds that is evidence for a formal charge of DPBD ligand of −2 in complex 1. However, the expected distribution of the C-C bond of the diene fragment as long—short—long is not realized.     

Synthesis and characterization of (C5H9C9H6)2Yb(THF)2(II) (1) and [(C5H9C5H4)2Yb(THF)]2O2 (2), and ring-opening polymerization of lactones with 1

Reaction of YbI₂ with two equivalents of cyclopentylindenyl lithium (C₅H₉C₉H₆Li) affords ytterbium(II) substituted indenyl complex (C₅H₉C₉H₆)₂Yb(THF)₂ (1) which shows high activity to ring-opening polymerization (ROP) of lactones. The reaction between YbI₂ and cyclopentylcyclopentadienyl sodium (C₅H₉C₅H₄Na) gives complex [(C₅H₉C₅H₄)₂Yb(THF)]₂O₂ (2) in the presence of a trace amount of O₂, the molecular structure of which comprises two (C₅H₉C₅H₄)₂Yb(THF) bridged by an asymmetric O₂ unit. The O₂ unit and ytterbium atoms define a plane that contains a C_i symmetry center.     

Metal carbonyl complexes of 3,5-dimethylaceheptylene. Synthesis and molecular structures of (C14H8Me2)Mn2(CO)6 and (C14H8Me2)Fe3(CO)8

The reactions of the non-alternant polycyclic aromatic hydrocarbon 3,5-dimethylaceheptylene, C₁₄H₈Me₂, with various transition metal carbonyls and the molecular geometry of the compounds (C₁₄H₈Me₂)Mn₂(CO)₆ and (C₁₄H₈Me₂)Fe₃(CO)₈ is shown.     

Synthesis, structural characterization and reactivity of the amino borane 1-(NPh2)-2-[B(C6F5)2]C6H4

The bright red title compound 1 was synthesized from (2-lithiophenyl)diphenylamine and bis(pentafluorophenyl)boron chloride. Its reactions with small acids like H₂O and HCl proceeded easily giving zwitterionic compounds. For 1 and its water adduct 2 the crystal structures were determined, the latter featuring an ammonium borate structure containing a short intramolecular hydrogen bond bridge. Treatment of 1 with Jutzi's acid, [H(OEt₂)₂][B(C₆F₅)₄], did not result in protonation of the nitrogen, but reaction of 1 with LiH in the presence of 12-crown-4, led to the isolation of the aminoborate [1-(Ph₂N)-2-{B(H)(C₆F₅)₂}C₆H₄][Li(12-crown-4)] (3). Borohydride 3 reacted with Jutzi's acid to regenerate 1 and liberate hydrogen.     

Novel rhenium(III) complexes with the picolinate ligand: Synthesis,spectroscopic investigations,X-ray structures and DFT calculations for [ReX2(pic)(PPh3)2] complexes

The paper presents a combined experimental and computational study of novel rhenium(III) complexes with the picolinate ligand – [ReCl₂(pic)(PPh₃)₂] (1) and [ReBr₂(pic)(PPh₃)₂] (2). Both complexes 1 and 2 have been characterised spectroscopically and structurally (by single-crystal X-ray diffraction). Complex 1 has been additionally studied by magnetic measurement. The magnetic behavior is characteristic of a mononuclear d⁴ low-spin octahedral Re(III) complex (³T_1g ground state) and arises because of the large spin–orbit coupling (ζ = 2500 cm⁻¹), which gives a diamagnetic ground state. DFT and time-dependent (TD)DFT calculations have been carried out for complex 1, and UV–vis spectra of the [ReX₂(pic)(PPh₃)₂] compounds have been discussed on this basis.