Nouvell préparation,propriétés electrochimiques et etude structurale des phosphaferrocenes η5-C5Me5Fe-η5-PC4(R4)

A new synthesis of phosphaferrocenes is described. It involves nucleophilic attack of a phospholyl anion on a metastable cyclopentadienyliron acetylacetonate. The monoelectronic oxidation of the phosphaferrocenes thus obtained has been studied by cyclic voltammetry in various solvents. The X-ray structures of [η⁵-C₅Me₅Fe-η⁵-PC₄(C₆H₅)₄] is discussed and compared with the structure of [η⁵-C₅H₅Fe-η⁵-PC₄H₂(CH₃)₂].     

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.     

过渡金属μ3-E立方烷簇合物(η ^5-C5H5)4Fe4(μ3-Se)4及 (η ^5-RC5H4) 4Cr4(μ3-S)4的合成与表征

通过 (η5 C5H5) 2 Fe2 (CO) 4和硒粉在沸腾的甲苯中反应可制得含 μ3 Se的立方烷簇合物 (η5 C5H5) 4Fe4 (μ3 Se) 4(1) ,而由 (η5 RC5H4 ) 2 Cr2 (CO) 4S在甲苯中回流可制得含 μ3 S的立方烷簇合物 (η5 RC5H4 ) 4Cr4 (μ3 S) 4(2 ,R =COMe ;3,R =CO2 Me)。企图通过 (η5 EtO2 CC5H4 ) 2 Fe2 (CO) 4(5 )和硫黄制备 μ3 S立方烷簇合物 (η5 EtO2 CC5H4 ) 4Fe4 (μ3 S) 4(6 )未获成功 ,其中 5是由 η5 EtO2 CC5H4 Fe(CO) 2 Na与 η5 EtO2 CC5H4 Fe(CO) 2 I (4 )缩合制得。新化合物 1～ 5经元素分析 ,IR和1 HNMR光谱表征     

Crystal structure of twinned (η5-C5(CH3)4CF3) (η5-C5(CH3)5)Ru

The substituted sandwich complex crystallizes in monoclinic space groupP2₁/m withZ=2. Twinning to the (001) direction with the special conditionc ^*/4a ^* = cos ^* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l=2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged atR = 0.040,R _w =0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of decamethylruthenocene.     

Synthesis and Crystal Structure of Spiro[1-bromo(S)-4-(R)-hydroxy-5-oxa-6-oxo-bicyclo[3.1.0]hexane-2,2''''-(3''''-diethyl-α-(S)-4''''''''-Cl-benzyloxyphosphonyl-4''''-(1R,2S,5R)-menthyloxybutyrolactone)]

1 INTRODUCTION In recent years, phosphorus compounds havebeen playing an important role in the new “high-tech” areas including life science and industrial te-chnology[1, .At the same time, the asymmetric syn- 2]thesis of various natural compounds containing cyc-lopropane components and organophosphorus grouphas attracted much attention due to their special bio-logical functions and antibiological activities[3～5].Despite the great advances in these areas, no novelapproach to the efficien…     

Crystal and Molecular Structure of(η~5-C_5H_5)_2Yb(NC_4H_4)(OC_4H_8)

ＣｒｙｓｔａｌａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆ（η~５－Ｃ_５Ｈ_５）_２Ｙｂ（ＮＣ_４Ｈ_４）（ＯＣ_４Ｈ_８）ＷａｎｇＳｈａｏ－Ｗｕ；ＹｕＹｏｎｇ－Ｆｅｉ；ＨｕＪｉ－ｐｉｎｇ；ＹｅＺｈｏｎｇ－Ｗｅｎ（ＩｎｓｔｉｔｕｔｅｏｆＯｒｇａｎｉｃＣｈ...     

A homometallic tricapped cubane cluster: [(Cp*Mo)4B4H4(μ4-BH)3] (Cp* = η5-C5Me5)

The reaction of [Cp*MoCl(4)] with an excess of LiBH(4), followed by thermolysis with tellurium powder in toluene, afforded a tricapped cubane cluster, [(Cp*Mo)(4)B(4)H(4)(μ(4)-BH)(3)] (1), which represents an unprecedented metal-rich metallaborane cluster with a cubane core containing 58 cluster valence electrons (cve) and three metal-metal bonds.     

Trans hexaco-ordinate complexes of copper(II) and nickel(II) with 4(5)-hydroxymethyl-5(4)-methylimidazole—crystal structure and physico-chemical properties

Trans complexes of Cu(II) and Ni(II) with 4-hydroxymethyl-5-methylimidazole (L), of the general formula [ML₄](NO₃)₂ have been obtained. The complexes were characterized by single X-ray diffraction, elemental analysis, EPR spectroscopy, IR, FIR and Vis–NIR spectra. In these co-ordination compounds, the azole ligand has a dual nature. Two of these molecules are monodentate, co-ordinated through the ‘3’ ‘pyridynic’ nitrogen atom of the imidazole ring, while the remaining two are bidentate ligands, the oxygen atom of the CH₂OH group being another electron donor (giving CuN₄O₂ and NiN₄O₂ chromophores). The structure of both chromophores is described by a slightly distorted tetragonal bipyramid. The stability constants and structures of the Cu(II) and Ni(II) complexes with the studied ligand (4-CH₂OH5-CH₃im) in aqueous solution have been determined by potentiometric and spectrophotometric methods. The stability of the transition metal complexes of 4-CH₂OH5-CH₃im depends on the presence of the hydroxymethyl group, the oxygen atom of which interacts with the metal-ion.     

钼铁混合金属原子簇化合物[(η5-C5H5)4Mo4Fe2(μ3-S)5(CO)5]的合成和结构

(η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5 have been prepared from (η~5-C_5H_5)_2Mo_2(CO)_6 and Fe_8S_2(CO)_9 under toluene reflux for 14.5 hrs.The crystal and molecular structures of (η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5 were studied by X-ray structure analysis. The Crystallographic data are as follows: monoclinic, space group P2_1/n, unit cell: a=1.0589(4), b=1.7260(4), c=1.8963(4) nm, β=101.44(2)°, V=3.3967 nm, D_c=2.06 gcm~(-3) for Z=4, X-ray data were obtained over the range of 2°<2θ<50° via the ω-2θ scan mode with MoKα radiation on an Enraf-Nonius CAD4 diffractometer. The structure was solved by direct method (MULTAN) and refined by full matrix least-squares techniques for 3993 reflections with I>2σ(I), The final R=0.081. Figure 1 illustrates the configuration of the molecule (η~5-C_5H_5)_4Mo_4Fe_2(μ_3-S)_5(CO)_5, composing of a cubane-like (FeMo_3S_4) core and a trigonal pyramid (MoFe_2S) core, which linked by sharing Fe(1) atom.     

Synthesis of the first anionic derivatives of Hf(CO)7: [(C5h5)Hf(CO)4]− and [(C5Me5)Hf(CO)4]−

Potassium naphthalenide reductions of [(C₅R₅)HfCl₃] (R  H, Me) in 1,2-dimethoxyethane at −60°C followed by carbonylation at atmospheric pressure provide 25–50% isolated yields of the first examples of carbonyl anions of hafnium(0), [(C₅H₅)Hf(Co)₄]⁻ and [(C₅Me₅)Hf(CO)₄]⁻. These were isolated as tetraethylammonium salts as well as K(cryptand-2.2.2) and K(15-Crown-5)₂⁺ salts for the latter anion and now represent two of only four presently known Hf⁰ carbonyls. They were characterized by elemental analyses, IR and ¹H and ¹³C NMR spectra.     

Synthèse et réactivité des dérivés de la 2,3-dihydro-3-hydroxy-2-phényl-1,5-benzothiazépin-4(5H)-one

New 1,5-benzothiazepinone derivatives have been synthesized. The cycloaddition of benzylazide with 5-propargyl-1,5-benzothiazepinone 7 gave compounds 9 and 10. The 1,5-benzothiazepinone 8 reacts with hydrazine to give 1,5-benzothiazepinone 11, which gave in hot acetic acid compound 12. The reaction of 3-chloro-1,5-benzothiazepinones 13, 14 or 15 with nucleophiles in DMF afforded the 2-benzylidenebenzothiazin-3-ones 16 and 17. The tosylate 18 gave the 1,5-benzothiazepinone 19 by reaction with N₃TMS in the presence of CsF in DMF.     

3-(N)-4-(Pyrazolo-4′,5′)-chinolin

Zusammenfassung Da bei Wiederholung der vonK. Eiter undMaria Nagy angegebenen Darstellung der Verbindung I diese in 59% iger Ausbeute erhalten werden konnte, wurde die Behauptung vonD. W. Ockenden undK. Schofield, wonach die Verbindung I nach unseren Angaben nicht herzustellen war, widerlegt.Weiters konnte bewiesen werden, daß eine vonSchofield undTheobald als 3-(Pyridyl-x)-lepidin bezeichnete Verbindung in Wirklichkeit die Verbindung I ist.     

一种新型的混合金属原子簇化合物(η^5-C5H5)4Mo4Fe2-(μ3-S)5(CO)5的合成和晶体结构

用(η^5-C5H5)2Mo2(CO)6和Fe3S2(CO)9在甲苯中的反应制备了一种新型混合金属原子簇化合物(η^5-C5H5)4Mo4Fe2-(μ3-S)5(CO)5.并用X-射线结构分析测定了它的晶体结构和分子结构.结果表明原子簇的骨架是由[FeMo3S4]的类立方烷孪合[MoFe2S]的三角锥,它们之间共用一个Fe原子.     

Phosphonates α-silylés (RO)2P(O)CR1R2SiR3R4R5 et α,α-disilylés (RO)2P(O)CR1[Si(CH3)3]2; preparation et propriétés

Phosphonoalkylation of trisubstituted chlorosilanes in the presence of excess i-Pr₂NLi has been examined to establish the steric acid and electrophilic properties of each silane. A similar sequence has been developed for the introduction of two Si(CH₃)₃ groups. The SiC bond cleavage clearly demonstrates the protecting effect of trisubstituted silyl groups; but the silyl groups do not influence the formation of vinylphosphonates in the Peterson reaction.     

Etude vibrationnelle de la phase II des hydrogénodisulfates de triammonium, (NH4)3H(SO4)2 et (ND4)3D(SO4)2

The i.r. and Raman spectra of room temperature phase (phase II) of (NH₄)₃H(SO₄)₂ and (ND₄)₃D(SO₄)₂ as polycrystalline samples and single crystals have been investigated between 4000 and 30 cm⁻¹. An assignment of internal and external modes is given in terms of group frequencies and symmetry types. This crystal contains non-centrosymmetric dimers (SO₄HSO₄)³⁻ where sulphate ions are associated by strong asymmetric OH … O hydrogen bonds; they are characterized by two strong Raman bands at 1078 and 966 cm⁻¹, and a νOH frequency at about 1250 cm⁻¹. The acidic proton is statistically disordered around the crystallographic symmetry centre while all of the NH⁺₄ ions show an important dynamical orientational disorder.     

SYNTHSIS OF 5-CYANO-2-(4-n-PENTYL-4-BIPHENYLYL)-PYRIMIDINE

Condensation of substituted diethyl-malonates withphenylamidine hydrochloride give liquid crystals with a pyrimidinering,which then subjeet graup transformation to give thetitle compound—5-cyano-2-(4-n-peatyl-4-biphenylyl)pyrimidine in high yield.     

Synthesis and structures of the η5-C5H5Cl(CO)2W-η1,η5-(PPh2)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 and MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3 complexes

The metallation of the η⁵-C₅H₅(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex with BuⁿLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph₂PCl afforded the η⁵-Ph₂PC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex. The reaction of the latter with η⁵-C₅H₅(CO)₃WCl in the presence of Me₃NO produced the trinuclear complex η⁵-C₅H₅Cl(CO)₂W-η¹,η⁵-(Ph₂P)C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃. The structure of the latter complex was established by IR, UV, and 1H and ³¹P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl₃ with three equivalents of LiC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃ gave the hexanuclear complex MeSi[C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃]₃.     

Synthesis and Crystal Structure of Chiral Spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyrolactam-6-oxo-dirings[3.1.0]hexane-2,3′-(4′-diphenylcarbinol-5′-menthyloxy-butyrolatone)}

A novel compound of chiral spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyro-lactam-6-oxo-dirings3.1.0hexane-2,3′-(4′-diphenylcarbinol-5′-menthyloxy-butyrolatone)} was synthesized via tandem nucleophilic substitution reaction under mild conditions=and its structure was determined by IR =1H NMR=elemental analysis and X-ray diffraction.The crystal structure of this compound is of monoclinic system=space group P21 with a=9.7356(9)=b=12.2760(12)=c=14.9577(14)=β=101.0300(10)°=Mr=680.66=Z=2=V=1754.6(3)3=Dc=1.288 g/cm3=μ(MoKα)=1.216 mm-1=F(000)=716=the final R=0.0434 and wR=0.0996.