Synthesis and Anti-inflammatory Action of （η-C5H5 ）2Ti（ Sal）2 and （η-C5H5 ）2Ti（Clo）2

IntroductionSince K pf[1]discovered that dicyclopenta die-nyltitanium dichloride possesses antitumour action in1979,a large number of cyclopentadienyltitanium com-plexes with different substituents have been synthe-sized[2,3].The experimental data reveal …     

A convenient synthesis of Fe(CO)2(η-S2CNMe2)2 and Fe(η-S2CNMe2)2 from the monodentate dithiocarbamato derivative, [(η-C5H5)(CO)3W(η-SCSNMe2)] and Fe2(CO)9

A high yield synthesis of the carbonyl dithiocarbamato derivative Fe(CO)₂(η²-S₂CNMe₂)₂ and Fe(η²-S₂CNMe₂)₂ by photolysis with visible light of solutions containing Fe₂(CO)₉ or Fe₃(CO)₁₂ and [(η⁵-C₅H₅)(CO)₃W(η¹-SCSNMe₂)] is reported.     

新型配合物Mn2Hg4(SCN)12的合成与晶体结构分析

A new inorganic coordination compound Mn₂Hg₄(SCN)₁₂ was synthesized. The grown crystals were characterized by elemental analysis, infrared spectroscopic analysis and powder crystal X-ray diffraction in detail. The crystal structure of Mn₂Hg₄(SCN)₁₂ was determined by single-crystal X-ray diffraction. It belongs to monoclinic system, P2₁/c space group. The cell dimensions are: a=1.171 6 nm, b=1.431 05 nm, c=2.105 1 nm, β=100.738°, and Z=4. In the structure of it, half of Mn²⁺ cations have five-coordinate number, and other half of Mn²⁺ cations have six-coordinate number; 3/4 of Hg²⁺ cations are coordinated by four SCN^-, 1/4 of Hg²⁺ cations are coordinated by three SCN^- and one NCS^-, all the coordination geometry of Hg²⁺ show slightly distorted tetrahedrons. CCDC: 244939.     

Synthesis and structural characterization of (μ-H)2RU3(CO)9(μ3-η-C8H12) and (μ-H)RU3(CO)9(μ3-η-C12H19)

The reaction between Ru₃(CO)₁₂ and a cyclic olefin (cis-cyclooctene or trans-cyclododecene) at 100 °C for several hours gives the title compounds (μ-H)₂RU₃(CO)₉(μ₃-η²-C₈H₁₂) (1), and (μ-H)RU₃(CO)₉(μ₃-η³-C₁₂H₁₉) (2), both of which have been characterized by X-ray diffraction studies, IR and NMR spectral measurements and elemental analysis. The prolonged reaction between Ru₃(CO)₁₂ and cis-cyclooctene gives compound HRu₃(CO)₉(C₈H₁₁) (3). Compound 3 has been characterized with IR and NMR spectral analyses. In 1 the cyclooctene ring is linked via a μ₃-η²-alkyne type of bonding to the face of the Ru₃ cluster. It is formally σ-bonded to two of the three Ru atoms and π-bonded to the third Ru. The two hydrides in 1 are bridging Ru---Ru bonds. In 2 the cyclododecene ring is bonded to the Ru₃ face via the μ₃-η³-CCHC linkage. There are two formal σ-bonds from the allyl part to the hydrido-bridged Ru atoms and the η³-allyl linkage to the third Ru atom.     

Synthesis,spectroscopic and structural investigation of Zn(NCS)2(nicotinamide)2 and [Hg(SCN)2(nicotinamide)]n

Zinc(II) and mercury(II) thiocyanate complexes with nicotinamide, bis(nicotinamide-N)-bis(thiocyanato-N)zinc(II) (1) and catena-[nicotinamide-N-(μ-thiocyanato-S,N)(thiocyanato-S)mercury(II)] (2), have been prepared and characterized by spectroscopic, thermal and X-ray crystallographic methods. The vibrational bands of diagnostic value are compared to the values of the free ligand and the data are in good correlation with the X-ray results. Centrosymmetrical hydrogen bonded dimers are found, R₂²(10) in 1 and R₂²(8) in 2.     

Imido complexes of molybdenum and tungsten(VI); X-ray crystal structure of cis-(η-CF3SO3)2 W(NBu)2(NH2Bu)2

The synthesis of the homoleptic molybdenum imido compound Li₂Mo(NBu^t)₄ is reported. The complexes M (NBu^t)₂(NHBu^t)₂ (M = Mo, W) can be protonated with various strong acids giving neutral species. The X-ray crystal structure of the tungsten complex W (NBu^t)₂(NH₂Bu^t)₂ (SO₃CF₃)₂ confirms the presence of O-coordinated cis- CF₃SO₃ groups.     

Preparation, structures, and haptotropic rearrangement of novel dinuclear ruthenium complexes, (μ2,η:η-guaiazulene)Ru2(CO)4(CNR)

Novel isonitrile derivatives of a diruthenium carbonyl complex, (μ₂,η³:η⁵-guaiazulene)Ru₂(CO)₅ (2), were synthesized by substitution of a CO ligand by an isonitrile, and were subjected to studies on thermal and photochemical haptotropic interconversion. Treatment of 2 (a 45:55 mixture of two haptotropic isomers, 2-A and 2-B) with RNC at room temperature resulted in coordination of RNC and alternation of the coordination mode of the guaiazulene ligand to form (μ₂,η¹:η⁵-guaiazulene)Ru₂(CO)₅(CNR), 5d–5f, [5d; R=^tBu, 5e; 2,4,6-Me₃C₆H₂, or 5f; 2,6-ⁱPr₂C₆H₃] in moderate to good yields. Thermal dissociation of a CO ligand from 5 at 60 °C resulted in quantitative formation of a desirable isonitrile analogue of 2, (μ₂,η³:η⁵-guaiazulene)Ru₂(CO)₄(CNR), 4d–4f, [4d; R=^tBu, 4e; 2,4,6-Me₃C₆H₂, or 4f; 2,6-ⁱPr₂C₆H₃], as a 1:1 mixture of the two haptotropic isomers. A direct synthetic route from 2 to 4d–4f was alternatively discovered; treatment of 2 with one equivalent of RNC at 60 °C gave 4d–4f in moderate yields. All of the new compounds were characterized by spectroscopy, and structures of 5d (R=^tBu) and 4d-A (R=^tBu) were determined by crystallography. Thermal and photochemical interconversion between the two haptotropic isomers of 4d–4f revealed that the isomer ratios in the thermal equilibrium and in the photostatic state were in the range of 48:52–54:46.     

Synthesis of [(μ-RS)(μ-S){Fe2(CO)6}2(μ4-S)] and their reactivity toward electrophiles

Reaction of the Et₃NH⁺ salts of the [(μ-RS)(μ-CO)Fe₂(CO)₆]⁻ anions (R=Bu^t, Ph or PhCH₂) with (μ-S₂)Fe₂(CO)₆ gives reactive intermediates [(μ-RS)(μ-S){Fe₂(CO)₆}₂(μ₄-S)]⁻. Reactions of the latter with alkyl halides, acid chlorides and Cp(CO)₂FeI have been studied. X-Ray structure of (μ-Bu^tS)(μ-PhCH₂S)[Fe₂(CO)₆]₂(μ₄-S) was determined.     

Improved syntheses of Ru(CO)2 (O3SCF3)2 (bidentate) complexes and their conversion into new [Ru(CO)2 (bidentate)2]2+ complexes

Reaction of the complexes Ru(CO)₂Cl₂L [L = 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen)] with trifluoromethanesulphonic acid under carefully controlled conditions yields Ru[cis-(CO)₂] [cis-(O₃SCF₃)₂] (bidentate complexes. From reactions of the trifluoromethanesulphonates with the appropriate bidentate ligands, the new complexes [cis-Ru(CO)₂-L(L′)]²⁺ (L as above; L′ = 4,4′-dimethyl-2,2′-bipyridyl or 4,4′-diisopropyl-2,2′-bipyridyl) as well as the known [_cis-Ru(CO)₂L₂]²⁺ and [cis-Ru(CO)₂bpy(phen)]²⁺ have been prepared.     

The thermal dissociation of the [Co(en)3](SCN)3 and [Co(en)3]I3 complexes

The thermal dissociation of the [Co(en)₃](SCN)₃ and [Co(en)₃]I₃ complexes was studied by thermogravimetry, differential thermal analysis, thermomagnetic analysis, pyrolytic techniques, evolved gas analysis, and mass spectrometry, in vacuo and nitrogen atmospheres. It was found that the [Co(en)₃](SCN)₃ complex dissociated in four steps:

It was not possible to elucidate the intermediate compounds formed in the thermal dissociation of the [Co(en)₃]I₃ complex.     

Electrochemical reduction of the dithiophosphate complexes CpFe(CO)2[η-SP(S)(OR)2], (Cp = η-C5H5 or η-C5Me5)

The reductive electrochemistry of compounds of the type CpFe(CO)₂L (Cp = η-C₅H₅, η-C₅Me₅; L = SP(S)(OEt)₂, SP(S)(OⁱPr)₂) has been examined by polarography, cylic voltammetry and coulometry. The first one-electron reduction step leads to a bond rupture process with formation of a mercury compound, [CpFe(CO)₂]₂Hg, at a mercury electrode and the corresponding dimer species at a platinum electrode. The second reduction step corresponds to the reduction of the dimer [CpFe(CO)₂]₂, except in the polarographic reduction of pentamethylcyclopentadienyl compounds.     

Cyclopentadienyl-ruthenium and -osmium chemistry : XXXIX. Syntheses of novel alkynyl-ruthenium complexes. X-Ray structures of two forms of {Ru(PPh3)2(η-C5H5)}2(μ-C4) and of Ru{CCC(O)Me}(PPh3)2(η-C5H5)

Reactions between [Ru(thf)(PPh₃)₂(η-C₅H₅)]⁺ and lithium acetylides have given further examples of substituted ethynylruthenium complexes that are useful precursors of allenylidene and cumulenylidene derivatives. From Li₂C₄, mono- and bi-nuclear ruthenium complexes were obtained: single-crystal X-ray studies have characterised two rotamers of {Ru(PPh₃)₂(η-C₅H₅)}₂(μ-C₄), which differ in the relative cis and trans orientations of the RuL_n groups. Protonation of Ru(CCCCH)(PPh₃)₂(η-C₅H₅) afforded the butatrienylidene cation [Ru(C=C=C=CH₂)(PPh₃)₂(η-C₅H₅)]⁺, which reacted readily with atmospheric moisture to give the acetylethynyl complex Ru{CCC(O)Me}(PPh₃)₂(η-C₅H₅), also fully characterised by an X-ray structural study.     

Joint x-ray and neutron diffraction structure analysis of [(μ-H)3Re3(CO)8{(EtO)2POP(OEt)2}2]

The compound [(μ-H)₃Re₃(CO)₈{(EtO)₂POP(OEt)₂}₂] crystallises in the monoclinic space group P2₁/c with a 18.053(6), b 16.211(5), c 14.800(3) Å, β = 102.41(2)°, and Z = 4. Simultaneous refinement of a single parameter set to fit 3212 X-Ray (sin θ/λ) > 0.352 Å⁻¹ and 1480 neutron data has led to final weighted residuals R_w(F) of 0.096 (X-Ray) and 0.095 (neutron). The molecule exhibits noncrystallographic C₂ symmetry, with two edges of the Re₃ triangle bridged by (OEt)₂POP(OEt)₂ ligands. The hydride ligands lie close to the trimetal plane with each hydride bridging an Re---Re vector. Average molecular parameters involving the hydride ligands are Re---H 1.812(17), Re---Re 3.282(17) Å, Re---H---Re 130(3) and H---Re---H 107.6(27)/dg. All eight carbonyl ligands are terminal, the ligand polyhedron being derived from that in H₃Re₃(CO)₁₂ by substitution of four axial carbonyls by two bidentate phosphite ligands.     

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.     

Syntheses and X-ray crystal structures of [Co(η-CO3)(NH3)4](NO3)·0.5H2O and [(NH3)3Co(μ-OH)2(μ-CO3)Co(NH3)3][NO3]2·H2O

[Co(η²-CO₃)(NH₃)₄](NO₃)·0.5H₂O and [(NH₃)₃Co(μ-OH)₂(μ-CO₃)Co(NH₃)₃][NO₃]₂·H₂O were prepared by prolonged aerial oxidation of a solution of Co(NO₃)₂·6H₂O and ammonium carbonate in aqueous ammonia. The formation of these side products highlights the richness of the chemistry of these systems and the possibility of by products if methods are not strictly adhered to. The X-ray crystal structures of [Co(η²-CO₃)(NH₃)₄][NO₃]·0.5H₂O and [(NH₃)₃Co(μ-OH)₂(μ-CO₃)Co(NH₃)₃][NO₃]₂·H₂O reveal a monomeric octahedral cobalt center with η²-bound CO₃²⁻ in the former, while the latter consists of a dimeric array where the two cobalt centers are bridged by two OH⁻ and one μ₂-CO₃²⁻ groups with three terminal NH₃ ligands for each Co center. In both complexes extensive hydrogen bonding interactions are evident.     

Synthesis and molecular structure of Ba5(μ5-OH)[μ3-OCH(CF3)2]4[μ2-OCH(CF3)2]4 [OCH(CF3)2](THF)4(H2O)·THF: a source of barium fluoride

The reaction between metallic barium and fluoroisopropanol or alcoholysis of [Ba(OPrⁱ)₂] produces a pentanuclear fluoroalkoxide. Its X-ray structure determination showed its formulation to correspond to Ba₅(μ₅-OH)[μ₃-OCH(CF₃)₂]₄[μ₂-OCH(CF₃)₂]₄ [OCH(CF₃)₂](THF)₄(H₂O)·THF. The metallic core is based on a square pyramid encapsulating an hydroxo ligand. In addition to the barium---alkoxide bonds [2.53(3)–2.86(3) Å] neutral O-donors, four THF [2.82(2)–2.86(3) Å] and one H₂O [2.79(3) Å] and secondary barium---fluorine interactions [2.99(2)–3.31(2) Å] ensure high coordination numbers, from 9 to 11 for the metal centers. Hydrogen bonding between the apical fluoroisopropoxide, the water molecule and one THF molecule, non-bonded to a metal center, accounts for the stability of the hydrate and illustrates the Lewis acidity of fluoroalkoxides. Thermal decomposition leads to BaF₂.     

Spin transition in [Fe(phen)2(NCS)2] and [Fe(bipy)2(NCS)2]: Hysteresis and effect of crystal quality

Detailed magnetic susceptibility measurements on the polycrystalline complexes [Fe(phen)₂(NCS)₂] (phen = 1.10-phenanthroline) and [Fe(bipy)₂(NCS)₂] (bipy = 2,2′-bipyridine) have revealed a narrow hysteresis in both systems indicative of a first-order nature of the spin transition ⁵T_2g(O_h) ? ¹ A_tg(O_h). The crystal quality, in particular crystal defects (through preparation or grinding), have been shown to influence strongly the spin transition behaviour.     

Synthesis and derivative chemistry of [Ru2(μ-PPh2) (μ-OH) 2(μ-p-cymene) 2]

The cationic diphenylphosphido-bridged compound [Ru₂(μ-PPh₂)(μ-OH)₂(η⁶-p-cymene)₂][PF₆) (2) has been prepared by reaction of the tri-μ-hydroxo complex [Ru₂(μ-OH)₃(η-p-cymene)₂][PF₆] (1) with diphenylphosphine. Complex 2 eliminates water on reaction with protic acids, incorporating the conjugate base of the added acid as a bridging ligand. Formic acid, acetic acid, phenol, and aniline react with 2 to give the monosubstituted compounds [Ru₂(μ-PPh₂)(μ-OH)(μ-L)(η⁶-p-cymene)₂]PF₆] (L = HCO₂, MeCO₂, OPh, or NHPH), whereas methanol, thiophenol, 1,2-benzenedithiol, hydrochloric acid and isopropanol afford the disubstituted derivatives [Ru₂(μ-PPh₂)(μ-L)₂(η⁶-p-cymene)₂]PF₆] (L = OMe, SPh, S₂C₆H₄, Cl, or H).     

Etude des propriétés de conduction électrique des polyphosphates: Li3Ba2(PO3)7, LiPb2(PO3)5, LiCs(PO3)2, et αLiK(PO3)2

The electrical conductivity of the crystallized polyphosphates Li₃Ba₂(PO₃)₇, LiPb₂(PO₃)₅, LiCs(PO₃)₂, and αLiK(PO₃)₂ has been determined at different temperatures by impedance spectroscopy. The conductivity, σ, spreads within a range of 1.59 × 10⁻⁸ to 1.79 × 10⁻⁷ S cm⁻¹ at 573 K, and from 1.71 × 10⁻⁵ to 9.86 × 10⁻⁴ S cm⁻¹ at 773 K. The transport should be assumed in the majority by the lithium ions with regard to the structural characteristics of these polyphosphates. The results are discussed and compared to the conductivity properties of other lithium ion conductors.