Synthesis and Structure of [Cu（OH）2（H2O）2（4—C5H4N—COOH）2]

1 INTRODUCTION Supramolecular chemistry and crystal engineering of coordination compounds have attracted considerable interests nowadays owing to the fascinating structural diversity and potential applications as functional materials[1,2]. Generally, architectures of supramolecules are formed through hydrogen bonds, ?- ?stacking interaction or other weak interactions between the molecules. Recently, many supramolecular compounds containing silver(I) and copper(II) species have been re-…     

Syntheses of Two Chiral Clusters [η5—C5H4C（NR）CH3]—RuNiM（CO）5（μ3—S）（R=NH—C6H3—2,4—（NO2）2,M=Mo,3;M=W,4）and the Single—crystal Structure of Cluster 3

1 INTRODUCTION The synthesis of chiral clusters containing four different atoms at the vertexes of the tetrahedron has been extensively studied because the chiral cluster can induce an asymmetric catalysis potentially[1]. Until now, many tetrahedron-type chiral clusters have been reported, but only a few of the reactions about the organic group in these clusters were investi- gated[2～4]. In this paper, we described the syntheses of clusters 3 and 4, and the structure of the former. 2 …     

Synthesis of Substituted Indenyl Lanthanide Chloride and Molecular Structure of[（C5H9C9H6）2Yb（μ—Cl）2Li（Et2O）2]

Reaction of anhydrous ytterbium trichlorides with 2 equiv.of cyclopentylindenyl lithium in THF solution,followed by removal of the solvent and crystallization of the porduct from diethyl ether,affords a crystal complex of the composition(C5H9C9H6)2Yb(μ-Cl)2Li(Et2O)2.Crystallographic analysis shows that the ytterbium coordinated by two cyclopentylindenly rings and lithium surrounded by two ether molecules are bridged by the two chlorine atoms and Yb,Li and two chlorine atoms form a plane.     

Preparation and Crystal Structure of Hetero—metal Clusters[η^5—C5H4C（O）CH2CH2C（O）OCH3]FeCoM（μ3—S）（CO）8（M=Mo or W）

1 INTRODUCTIONTransition metal clusters have been attracting intensive attention largely because they are suggested as active catalysts in a variety of homogeneous catalyzed reactions. However, no unequivocal proof exists that metal clusters themselves serve as the true catalysts among the catalytic process. In many cases it is known that fragments of the original clusters are the actual catalytic species. The unambiguous proof would be the use of a rigid chiral cluster to catalyze an asy…     

Synthesis and Crystal Structure of CoCl（ieaa）（C10H7—ieai）（C10H7NH2）

1 INTRODUCTION A number of isonitroso-b-diketones and isonitroso-b-ketoesters such as isonitrosoacetyl- acetone(Hiaa), isonitrosobenzoylacetone(Hiba) and isonitrosoethylacetoacetate (Hieaa) have been employed as reagents in spectrophotometric determination of iron, palladium and ruthenium[1]. Transition metal complexes of such ligands[2] are potential models for metal binding sites in ferroverdin[3]. They were found as dyes and light-absorbing agents for the acceleration of the sol…     

Cleavage of the Fe—Fe Bond of （Me2SiSiMe2） [η^5－C5H4Fe（CO）2]2 with Na／Hg and Molecular Structure of the Ring－Opened Complex

The reaction of the rifle cyclic complex (1) with sodium amalgam in THF resulted in the expected cleavage of the Fe-Fe bond to afford his-sodium salt ( Me2SiSiMe2 ) [η^5-C5H4Fe(CO)2]2 (4). The latter was not isolated and was used directly to react with MeI, PhCH2Cl, CH3C(O)Cl, PhC(O)Cl,Cy3SnCl (Cy= cyclohexyl) or Ph3SnCl to afford corresponding ring-opened derivatives (Me2SiSiMe2) [η^5-C5H4Fe(CO)2]2 [5, R=Me; 6, R=PhCH2; 7, R=CH3C(O); 8, R=PhC(O); 9, R = Cy3Sn or 10, R = Ph3Sn ]. The crystal and molecular structures of 10 were determined by X-ray diffraction analysis. The molecule took the desired ant/ conformation around the Si-Si bond. The length of the Si--Si bond is 0.2343(3)nm, which is essentially identical to that in the cyclic structure of 1[0.2346(4) tun]. This result unambiguously demonstrates that the Si--Si bond in the cyclic structure of 1 is not subject to obvious strain.     

Synthesis and Crystal Structure of Dichlorodianiline Palladium （Ⅱ） （C6H5NH2）2PdCl2

1 INTRODUCTION Palladium compounds have attracted much attention as a consequence of their application in homogeneous and heterogeneous catalyses[1]. For instance, palladium compounds are the most active catalysts for the carbonylation, such as palladium-catalyzed carbonylation of nitroarenes, aryl halides, alkyne and so on[2～4]. Some dramatic results in the homogeneous catalysis of the reactions of organic compounds, particularly the successful commercial exploitation of the Wacker on…     

Ansa‐Complexes of [Mn(η5‐C5H5)(η6‐C6H6)]: Preparation,Characterization, and Reactivity of [n]Manganoarenophanes (n=1, 2, 3)

We report the synthesis of [n]manganoarenophanes (n=1, 2) featuring boron, silicon, germanium, and tin as ansa‐bridging elements. Their preparation was achieved by salt‐elimination reactions of the dilithiated precursor [Mn(η⁵‐C₅H₄Li)(η⁶‐C₆H₅Li)]?pmdta (pmdta=N,N,N′,N′,N′′‐pentamethyldiethylenetriamine) with corresponding element dichlorides. Besides characterization by multinuclear NMR spectroscopy and elemental analysis, the identity of two single‐atom‐bridged derivatives, [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] and [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SiPh₂], could also be determined by X‐ray structural analysis. We investigated for the first time the reactivity of these ansa‐cyclopentadienyl–benzene manganese compounds. The reaction of the distannyl‐bridged complex [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)Sn₂tBu₄] with elemental sulfur was shown to proceed through the expected oxidative addition of the Sn?Sn bond to give a triatomic ansa‐bridge. The investigation of the ring‐opening polymerization (ROP) capability of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] with [Pt(PEt₃)₃] showed that an unexpected, unselective insertion into the C_ipso?Sn bonds of [Mn(η⁵‐C₅H₄)(η⁶‐C₆H₅)SntBu₂] had occurred.     

Synthese,Struktur und Reaktivität von η3‐1,2‐Diphosphaallylkomplexen sowie von [{(η5‐C5H5)(CO)2W–Co(CO)3}{μ‐AsCH(SiMe3)2}(μ‐CO)]

Syntheses, Structure and Reactivity of η³‐1,2‐Diphosphaallyl Complexes and [{(η⁵‐C₅H₅)(CO)₂W–Co(CO)₃}{μ‐AsCH(SiMe₃)₂}(μ‐CO)] Reaction of ClP=C(SiMe₂iPr)₂ ( 3 ) with Na[Mo(CO)₃(η⁵‐C₅H₅)] afforded the phosphavinylidene complex [(η⁵‐C₅H₅)(CO)₂Mo=P=C(SiMe₂iPr)₂] ( 4 ) which in situ was converted into the η¹‐1,2‐diphosphaallyl complex [η⁵‐(C₅H₅)(CO)₂Mo{η³‐tBuPPC(SiMe₂iPr)₂] ( 6 ) by treatment with the phosphaalkene tBuP=C(NMe₂)₂. The chloroarsanyl complexes [(η⁵‐C₅H₅)(CO)₃M–As(Cl)CH(SiMe₃)₂] [where M = Mo ( 9 ); M = W ( 10 )] resulted from the reaction of Na[M(CO)₃(η⁵‐C₅H₅)] (M = Mo, W) with Cl₂AsCH(SiMe₃)₂. The tungsten derivative 10 and Na[Co(CO)₄] underwent reaction to give the dinuclear μ‐arsinidene complex [(η⁵‐C₅H₅)(CO)₂W–Co(CO)₃{μ‐AsCH(SiMe₃)₂}(μ‐CO)] ( 11 ). Treatment of [(η⁵‐C₅H₅)(CO)₂Mo{η³‐tBuPPC(SiMe₃)₂}] ( 1 ) with an equimolar amount of ethereal HBF₄ gave rise to a 85/15 mixture of the saline complexes [(η⁵‐C₅H₅)(CO)₂Mo{η²‐tBu(H)P–P(F)CH(SiMe₃)₂}]BF₄ ( 18 ) and [Cp(CO)₂Mo{F₂PCH(SiMe₃)₂}(tBuPH₂)]BF₄ ( 19 ) by HF‐addition to the PC bond of the η³‐diphosphaallyl ligand and subsequent protonation ( 18 ) and/or scission of the PP bond by the acid ( 19 ). Consistently 19 was the sole product when 1 was allowed to react with an excess of ethereal HBF₄. The products 6 , 9 , 10 , 11 , 18 and 19 were characterized by means of spectroscopy (IR, ¹H‐, ¹³C{¹H}‐, ³¹P{¹H}‐NMR, MS). Moreover, the molecular structures of 6 , 11 and 18 were determined by X‐ray diffraction analysis.     

Synthesis,characterization, anti‐inflammatory and analgesic activity of transition metal complexes of 3‐[1‐(2‐hydroxyphenyl) ethylideamino]‐2‐phenyl‐3,4‐dihydroquinazolin‐4(3H)‐one

A new quinazolinone derivative, 3‐[1‐(2‐hydroxyphenyl)ethylideamino]‐2‐phenyl‐3,4‐dihydroquinazolin‐4(3H)‐one ( LH ) was synthesized by the condensation of 2‐hydroxyacetophenone‐2‐aminobenzoylhydrazone and benzaldehyde. The cyclization to form 1,2‐dihydroquinazolinone was confirmed by IR, 1D and 2D HETCOR studies. Coordination compounds of Co(II), Ni(II), Cu(II) and Zn(II) of LH were synthesized and characterized using various physico‐chemical studies like stoichiometric, conductivity, magnetic moment measurements and spectral techniques such as IR, NMR, UV‐vis and EPR spectroscopy. The elemental analysis and thermal studies suggested a general stoichiometry [M(HEPDQ)Cl] for all the complexes. A four‐coordinate geometry was assigned to all the complexes. The complexes along with the parent ligand were screened for their anti‐inflammatory activity, using carrageenan‐induced rat paw edema, and for their analgesic activity by Eddy's hot plate method. The activity of the ligand was enhanced on complexation with metal ions. This enhanced activity was attributed to the increased lipophilic nature of the complexes. Notable anti‐inflammatory activity was observed for Ni(II), Cu(II) and Zn(II) complexes. The analgesic activity of the ligand was greater than the standard at 60 min. and at a 10 mg kg⁻¹ dose, whereas the activity of Ni(II) and Cu(II) complexes at 10 mg kg⁻¹ dose was comparable with the standard used. Copyright © 2011 John Wiley & Sons, Ltd.     

Two New C19‐Diterpenoid Alkaloids with Anti‐inflammatory Activity from Aconitum iochanicum

Two new C₁₉ ‐diterpenoid alkaloids, 7,8‐epoxy‐franchetine ( 1 ) and N(19)‐en‐austroconitine A ( 2 ), were isolated from Aconitum iochanicum . Compound 1 was a new C₁₉ ‐diterpenoid alkaloid with a 7,8‐epoxy unit. Their structures were elucidated by comprehensive spectroscopic analyses including UV , IR , MS , 1D and 2D NMR . Biological activity tests indicated that two new compounds exhibited inhibitory activity against nitric oxide (NO ) production in LPS ‐activated RAW264 .7 macrophages. Compared with positive control, the two new compounds showed weak anti‐inflammatory effects with the inhibition rate of 27.3% and 29.2%, respectively.     

1,1′-Disubstituierte Titanocen-dithiolen-Chelate des Typs (η5-Me3EC5H4)2Ti(S2C2R2) (E = C,Si, Ge)

1,1′-Disubstituted Titanocene Dithiolene Chelates of Type (η⁵-Me₃EC₅H₄)₂Ti(S₂C₂R₂) (E = C, Si, Ge) Reaction of the titanocene dichlorides (η⁵-Me₃EC₅H₄)₂TiCl₂ (E = C, 1a ; E = Si, 1b ; E = Ge, 1c ) with the 1,2-dithiolates (NaS)₂C₂H₂, (NaS)₂C₂(CN)₂ or (LiS)₂C₆H₃Me-4 gave the new titanocene dithiolene chelates (η⁵-Me₃EC₅H₄)₂Ti(S₂C₂H₂) ( 2a–c ), (η⁵-Me₃EC₅H₄)₂Ti[S₂C₂(CN)₂] ( 3a–c ) and (η⁵-Me₃EC₅H₄)₂Ti(S₂C₆H₃Me-4) ( 4a–c ). These have been characterized by ¹H NMR, IR, and mass spectroscopy, and have been compared with the unsubstituted η⁵-C₅H₅ analogues 2d, 3d and 4d . Activation energies for the chelate ring inversion in solution of 2a–c, 3a–d and 4a–c have been estimated by temperature-dependent ¹H NMR spectroscopy.     

Preparation and Reactivity of Mo(NCMe)(η2‐C2Ph2)2(η4‐C4Ph4)

Reaction of Mo(CO)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) and Me₃NO in acetonitrile solvent affords Mo(NCMe)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) 1 . Compound 1 reacts with trimethylphosphine to produce Mo(PMe₃)(η²‐C₂Ph₂)₂(η⁴‐C₄Ph₄) 2 , or reacts with diphenylacetylene to produce (η⁵‐C₅Ph₅)₂Mo 3 and Mo(η²‐O₂CPh)(η⁴‐C₄Ph₄H)(η⁴‐C₄Ph₄) 4 . The molecular structures of 1, 2 and 4 have been determined by an X‐ray diffraction study.     

Synthesis,Characterization and Reactivity of the Tricarbonyl(formylcycloheptatrienyl)iron‐Anion [(η3‐C7H6CHO)Fe(CO)3]−

Deprotonation of the readily available organometallic aldehyde derivative [(η⁴‐C₇H₇CHO)Fe(CO)₃] ( 2 ) with NaN(SiMe₃)₂ in benzene solution at ambient temperature afforded the anionic formylcycloheptatrienyl complex Na[(η³‐C₇H₆CHO)Fe(CO)₃] ( 3 ). The anion is fluxional in solution and displays a unique ambident reactivity towards electrophiles (MeI, Me₃SiCl). New substituted [(η⁴‐RC₇H₆CHO)Fe(CO)₃] and [(η⁴‐heptafulvene)Fe(CO)₃] complexes have been identified as the products. Treatment of 3 with 0.5 equivalents of dimeric [(COD)RhCl]₂ (COD = 1,5‐cyclooctadiene) afforded the functionalized Fe‐Rh cycloheptatrienyl complex [(μ‐C₇H₆CHO)(CO)₃FeRh(COD)] ( 7 ) in up to 86 % yield. Carbonylation of 7 under an atmosphere of CO led to facile conversion to the heterobimetallic pentacarbonyl derivative [(μ‐C₇H₆CHO)(CO)₃FeRh(CO)₂] ( 8 ), which is also accessible in lower yield from the direct reaction of 3 with [Rh(CO)₂Cl]₂.     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.