三核锇原子簇中μ,η~2-乙烯配位基顺反异构化及其反应动力学研究

含氢原子簇化合物H_2Os_3(CO)_(10)与乙炔反应生成顺式加成物[Os_3H(μ,η~2-CH=CH_2)(CO)_(10)]。本文首次报道高含量氘代原子簇D_2Os_3(CO)_(10)与乙炔反应生成合乙烯配位基的氘代原子簇[Os_3D(μ,η~2-CH=CHD)(CO)_(10)],H_2Os_3(CO)_(10)与氘代乙炔反应生成[Os_3H(μ,η~2-CD=CDH)(CO)_(10)],它们在微量亲核试剂吡啶作用下发生μ,η~2-乙烯配位基的顺反异构反应。本文用同位素氘代和~1H,~2H NMR动态波谱联用方法,研究了上述反应和异构化过程,提出了顺反异构化的核磁共振动态波谱证据、反应机理和动力学数据。     

Reactivity of Fe_3(CO)_(12) with Alkynes R-C≡C-R': Syntheses and Crystal Structures of Substituted Cyclic Ketones and Carbonyl Iron Complexes

The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3(CO)_(12) with R-C≡C-R'(R = Fc(Ferrocenyl); R′ = Ph(Phenyl), Fc, H). The hexacarbonyldiiron cluster with ferracyclopentadiene ring(μ_2, η~4-C_4Ph_4)Fe_2(CO)_6(1) and one tetraphenyl substituted cyclopentadienone(Ph_4C_4CO)(2) were simultaneously obtained by the reaction of Fe_3(CO)_(12) with alkyne(Ph-C≡C-Ph). Only one ferrole cluster(μ_2, η~4-C_4Fc_2H_2)Fe_2(CO)_6(3) was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex(η~4-C_4Fc_4CO)Fe(CO)_3(4) and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3(CO)_2](5) were obtained by using Fc-C≡C-Fc as alkyne. A new complex(η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one)-tricarbonyl iron(η~4-C_4Ph_2Fc_2CO)Fe(CO)_3(6) was synthesized by the reaction of Fe_3(CO)_(12) with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.     

Synthesis, Reaction and Structures of Functionally Substituted η~5-Cyclopentadienyl Compounds With Cr≡S Triple Bond [η~5-RC_5H_4Cr(CO)_2]_2S (R=CH_3C(O),CH_3O_2C,C-2H_5O_2C,CH_3CH(OH),CO_2H)

[η_5-OH_3C(O)C_5H_4Cr(CO)_2]_2S 1, [η~5-CH_3O_2CC_5H_4Cr(CO)_2]_2S 2 and [η~5-C_2H_5O_2CC_5H_4Cr(CO)_2]_2S 3 were prepared by the reactions of corresponding sodium salts of functional η~5-cyclopentadienyl-tricarbonylchromium anions with SOCl_2. Reduction of 1 with NaBH_4 prdouced [η~5-CH_3CH(OH)C_5H_4Cr(CO)_2]_2S 4, while saponification of 2 followed by acidification and recrystallization from acetone afforded [η~5-HO_2CC_5H_4Cr(CO)_2]_2S·nCH_3C·(O)CH_3 5. 1—5 are a new class of Cr≡S triple bond compounds containing functional organic group on the cyclopentadienyl ring. A single-crystal X-ray diffraction analysis of 1 revealed that it consists of two identical organometallic fragments η~5-CH_3C(O)C_5H_4Cr(CO)_2 joined together by a sulfur atom via triple bonds. The geometry of structural unit Cr≡S≡Cr belongs to linearity and the average triple bond length of Cr≡S is 2.072(?).     

A new route to prepare the mixed oxo-ethylidynecapped trinuclear tungsten(Ⅳ)cluster and the crystal structure of H_2Na_3[W_3O(CCH_3)(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5H_2O

The synthesis and the structural characterization of the title compound H_2Na_3[W_3O(CCH_3)-(O_2CCH_3)_6(H_2O)_3][H_2W_(12)O_(40)]·13.5 H_2O are described.It is known that the mixed oxo-ethylidyne-capped tritungsten cluster can be obtained by Zn dust reduction of Na_2WO_4·2H_2O in acetic anhydride.The title compound has been characterized by X-ray diffraction,UV/VIS and ~1H NMR spectra.The tungsten atoms in the cluster cation and anion are in the oxidation states of W(IV)and W(VI)respectively.The crystal is rhombohedral with the space group R32,a=17.058(3),c=49.665(9),γ=120°,V=12516(9)~3,Z=6,final R=0.037 for 2071 reflections with I≥3σ(I).Boththe cluster cation and anion have a C_3 symmetry.The important interatomic distances in angstroms forthe cluster cation are:W—W,2.730(2);W—μ_3-O,2.00;W—O(carboxyl),2.12;W—O_t,2.18(2).     

SYNTHESIS,CHARACTERIZATION AND CRYSTAL STRUCTURES OF η~5-CH_3C_5H_4)M(CO)_2NO AND(η~5-CH_3C_5H_4)M(μ_3-NH)(μ_2-NO)(μ_2-CO)Fe_2(CO)_6(M=Mo or W)

Synthesis of complexes(η~5-CH_3C_5H_4)M(CO)_2NO(M=Mo,I;M=W,II)and clusters(η~5-CH_3C_5H_4)M(μ~3-NH)(μ~2-NO) (μ~2-CO)Fe_2(CO)_6(M=Mo,III:M=W,IV),based on the reaction of (η~5-C5_H_4)M(CO)_3Cl with Na[Fe(CO)_3NO] at room tem-perature,have been demonstrated,The crystal structures of II and IV arealso presented.     

STUDIES ON ORGANOMETALLIC COMPOUNDS OF TITANIUM,ZIRCONIUM AND HAFNIUM——THE SYNTHESES AND PROPERTIES OF BIS (CYCLOPENTADIENYL) AND BIS (METHYLCYCLOPENTADIENYL) DI(ARYL)-METAL DERIVATIVES

Aryllithium reacts with Cp_2MCl_2 and Cp'_2 MCl_2 (C_p=η~5-C_5H_5, C_P′=η~5-CH_3C_5H_4:M=Ti, Zr, Hf) respectively to prepare a series of new bis (cyclopentadienyl), bis (methy-lcyclopentadienyl) diaryl derivatives of titanium, zirconium and hafnium. The hydrolysicreaction of these organometallic compounds are studied, the derivatives of zirconium andhafnium can be easily hydrolyzed with the exception of that of titanium. They react withhydrogen chloride, acetyl chloride, bromine and haloacids to form the respective bis(cyclo-pentadionyl) dihalides of these metals. The NMR and IR spectra were discussed in regardto the structure of (η~5--CH_3C_5H_4)_2 MAr_2 and (η~5--CH_3C_5H_4)_2 MX_2.     

UV LASER INITIATED STEREOSELECTIVE HOMOGENEOUS CATALYSIS POLYMERIZATION OF PHENYLACETYLENE

In this paper, the stereoselective homogeneous catalysis polymerization of phenylacetylene by using two kinds of catalysts W(CO)_5CH_3I and W(CO)_4I_2 produced from UV laser photolysis of W (CO)_6 in CH_3I, I_2—C_6H_6 and CHI_3—C_6H_6 respectively was studied. The effects of laser energy, laser irradiation time and lifetime of catalyst on the polymerization of phenylacetylene were discussed. The photoproducts of W (CO)_6 in CH_3I, I2—C_6H_6 and CHI_3—C_6I_6 were determined by IR spectra. The structures of polyphenylacetylene obtained by W (CO)_5CH_3I and W (CO)_4I_2 catalysts were characterized by IR spectra and ~1H NMR spectra.     

POLYMER-SUPPORTED CLUSTER II SYNTHESIS, CHARACTERIZATION AND CATALYTIC PROPERTIES OF POLYMERSUPPORTED HETEROPENTAMETALLIC CLUSTER FeCO3 (CO)12 (μ3-AuPph2CH2■-■)*

The polymer-supported cluster FeCo3 (CO)_(12) (μ3-AuPph_2 CH_2) (4) has been synthesized through reaction of CH_2 ph_2 PAuCl with the cluster anion FeCo_3 (CO)_(12)~-. They are characterized through IR spectra, electronic spectra and XPS, with homogenous analog FeCo_3 (CO)_(12) (μ3-AuPph_3) (3) as reference compound. The cluster (3) and the polymer-supported cluster (4) are good catalysts for hydroformylation of olefins. They have better activity and selectivity than the cluster (1) and (2).The supported cluster (4) is more stable and has catalytic activity at higher temperature than its homogeneous analog (3). From the metal core level binding energies in XPS and λ_(max) in electronic spectra, it is found that the metal-metal bonds in (4) are reinforced bypolymer supporter. The cluster (3) and (4) can be reused , and possibly do not fragment to one metal species in the course of catalytic reaction.     

SYNTHFESIS,STRUCTURE AND RFACTION OF TETRAMETHYL-DISILANDIYL DICYCLOPENTADIENYL TETRACARBONYL DI-IRON

The title compounds(Me_2SiSiMe_2)(η-RC_3H_3)Fe(CO)(μ-CO)_2(R:H(1a),Me(1b))wereprepared by heating a solution of RC_(?)H_4(Me_2SiSiMe_2)C_5H_4R and Fe(CO)_5 in xylene atreflux.(1a)and(1b)can convert into their isomers Me_2Si(η-RC_3H_3)Fe(CO)_2(?)2(R:H(2a),Me(2b))under the reaction conditions.The crystal and molecular structures of(1a),(2a)and(2b)were determined by X-ray diffraction.     

Novel Lanthanide Cluster Polymers Based on Cubane-like [Ln_4(OH)_4]~(8+) Clusters and Sulfate Anions

Two lanthanide-oxo-cluster polymers were synthesized by hydrothermal reaction using Ln_2O_3 as initial lanthanide materials:[Ln_4(SO_4)_4(OH)_4(H_2O)_7]·_4H_2O(Ln = Er 1,Ho 2),and characterized by PXRD,IR spectra,X-ray single-crystal diffraction,2D IR correlation spectra and UV-visible absorption spectra.Single-crystal X-ray analyses reveal that compounds 1 and 2 are isostructural,and they are both crystallized in the orthorhombic system Pccn space group.Compound 1 is a 3D lanthanide cluster polymer based on tetranuclear cubane-like [Er_4(μ_3-OH)_4]~(8+) cations and SO_4~(2-) anions.The overall structure of 1 can be assigned to 6-connected pcu-type topology with the point symbol of(4~(12).6~3).     

STUDY ON THE REACTIVITY OF TRICARBONYL(PENTAMETHYL-DISILANYL)CYCLOPENTADIENYL MOLYBDENUM ANION

Some reactions of the title anion were studied.Bythese reactions six molybdenum complexes were prepared.On reac-tion with 1,3-dibromopropane the anion yielded the cyclic carbenecomplex(η-C_5H_4Si_2Me_5)MoBr(CO)_2CO(CH_2)_2CH_2.The crystal and mole-cular structures of (η-C_5H_4Si_2Me_5)MoBr(CO)_3 and 〔(η-C_5H_4Si_2Me_5)Mo-(CO)_3〕_2 Were determined by X-ray crystallography.     

DYNAMIC NMR STUDIES ON [Li(2D)][Nd(η~3-C_3H_5)_4]

The dynamic ~1H and ~(13)C-NMR studies on [Li(2D)][Nd(η~8-C_3H_5)_4](D=dioxane)were reported The four allyls coordinated to Hd~(8+) ion areequivalent and hydrogens appear as three groups in ~1H-NMR spectra with theirchemical shifts changing with temperature.C_1 and Ca are equivalent showing thecharacteristic of η~2=-allyl.The paramagnetic shifts of carbons in allylsinduced by Nd~(2+) ere separated sucessfully.C_1 and C_3 located on thezero-dipolar cone.The content of contact shift is greater than that of dipolarslift to Co.     

STUDY OF CARBON MONOXIDE HYDROGENATION OVER SUPPORTED IRON CLUSTER CATALYSTS

Fe_3(CO)_(12)-derived Fe/r-AL_2O_3 and Fe/zeolite catalysts have higher catalytic activity than those derived from Fe(NO_3)_3. The existence of metal-metal bond in cluster species and the congruity of the adsorption of CO and H_2 are important for increasing the catalytic activity. Carbon deposition for Fe_5C(CO)_(15)-derived Fe/r-AL_2O_3 catalyst is discussed.     

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,(μ-pdt)Fe_2(CO)_5(Ph_2PCH_3)(pdt = SCH_2CH_2CH_2S),was obtained by the reaction of the parent complex(μ-pdt)Fe_2(CO)_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield(90%). The title complex was characterized by IR,~1H NMR,~(31)P{~1H} NMR and ~(13)C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals' interactions stabilize the solid state to form a three-dimensional network.     

Syntheses and Structures of Three Hybrid Materials Using Vanadium Polyoxoanions and Macrocyclic Copper Complex as Building Blocks

The reactions of the four-coordinated macrocyclic copper complex [CuL](ClO_4)_2(L = 1,4,8,11-tetraazacyclotetradecane) with NH_4VO_3 under different conditions gave three inorganic-organic hybrid materials of [CuL][VO_3]_2·2.33H_2O(1), [CuL]_3[V_(10)O_(28)]·8H_2O(2) and [Cu L]3[V_6O_(18)]·8H_2O(3). Single-crystal X-ray diffraction analyses reveal that three diverse vanadium polyoxoanions, [V_6O_(18)]6- ring, [V_(10)O_(28)]6- cluster, and [V_(12)O_(35)]~(10-) ring, were isolated from the same reactant NH_4VO_3 under different conditions. The [CuL]~(2+) bridges the [V10O28]6- clusters to form a two-dimensional sheet in 2, and link the [V_6O_(18)]~(6-) rings in 1 and [V_(12)O_(35)]~(10-) rings in 3 into three-dimensional frameworks, respectively.     

SYNTHESES OF TETRAHEDRAL METAL CLUSTER COMPOUNDS

The carbyne compound [Br(CO)_2(Py)_2Mo(≡CC_6H_5)] (Py=pyridine) (1a) reacts with Co_2 (CO)_8, Fe_2(CO)_9 and Mn_2 (CO)_(10) to give tetrahedral tri-metal cluster compounds Co_2Mo(μ_3-CC_6H_5)Br(CO)_8(Py)_2 (2), Fe_2Mo(μ_3-CC_6H_5) Br(CO)_9(Py)_2 (3) and Mn_2Mo(μ_3-CC_6H_5)Br(CO)_(10) (Py)_2 (4) respectively. Tri-metal cluster compound Co_2Mo(μ_3-CC_6H_5)Br(CO)_8-(bipy) (bipy=α,α'dipyridyl) (5) is prepared in a similar reaction sequence from [Br(CO)_2(bipy)Mo(≡CC_6H_5)] (1b) and Co_2(CO)_8. IR, ~1H and ~(13)C NMR spectral data of these compounds are reported and discussed. The crystal structure of compound (5) has been determined by X-ray diffraction.     

Isolation of New Disilanylene-bridged Bis（cyclopentadienyl）tetracarbonyldiiron Complexes and Molecular Structure of [η^5, η^5-C5H4SiMe（SiMePh2）C5H4]Fe2（CO）2（μ-CO）2

1,2-Diphenyl-1,2-dimethyldisilanylene-bridged bis-cyclopentadienyl complex[η~5,η~5-C_5H_4PhMeSiSiMePh-C_5H_4]Fe_2(CO)_2(μ-CO)_2(1)was synthesized by a modified procedure,from which the trans-isomer 1b that was pre-viously difficult to obtain has been isolated for the first time.More interestingly,two new regio-isomers[η~5,η~5C_5H_4SiMe(SiMePh_2)C_5H_4]Fe_2(CO)_2(μ-CO)_2(2)and [η~5,η~5-C_5H_4Me_2SiSiPh_2C_5H_4]Fe_2(CO)_2(μ-CO)_2(3)were occa-sionally obtained during above process,the novel structures of which opened up new options for further study ofthis type of Si—Si bond-containing transition metal complexes.The molecular structure of 2 has been determinedby the X-ray diffraction method.     

Synthesis,Characterization and Electrochemistry of 1,2-Bis(diphenylphosphino)benzene-chelated Diiron Ethane-1,2-dithiolate Tetracarbonyl Complex

In this paper, a novel diiron ethane-1,2-dithiolate complex [Fe_2(CO)_4{κ~2-(Ph_2P)_2(1,2-C_6H_4)}(μ-SCH_2CH_2S)] has been prepared and structurally characterized. Treatment of the parent complex [Fe_2(CO)_6(μ-SCH_2CH_2S)] with 1 equivalent of 1,2-bis(diphenylphosphino)benzene and Me_3NO?2H_2O as the oxidative agent gave the title complex in good yield. The title complex has been characterized by elemental analysis, IR, ~1H NMR, ~(31)P{~1H} NMR, ~(13)C{~1H} NMR spectroscopy, and X-ray crystallography. X-ray crystal structure of the title complex contains a butterfly diiron cluster with a bridging ethane-1,2-dithiolate, four terminal carbonyls, and a chelating 1,2-bis(diphenylphosphino)benzene. In addition, electrochemical studies revealed that the title complex can catalyze the reduction of protons to H_2 in the presence of acetic acid.     

Cleavage of the Fe-Fe Bond of(Me_2SiSiMe_2)[η~5-C_5H_4Fe(CO)_2]_2 with Na/Hg and Molecular Structure of the Ring-Opened Complex

The reaction of the title cyclic complex(1) with sodium amal-gam in THF resulted in the expected cleavage of the Fe--Febond to afford bis-sodium salt (Me_2SiSiMe_2) [η~5-C_5H_4Fe(CO)_2Na]_2 (4). The latter was not isolated and was used di-rectly to react with MeI, PhCH_2Cl, CH_3C(O)Cl, PhC(O)Cl,Cy_3SnCl (Cy=cyclohexyl) or Ph_3SnCl to afford correspondingring-opened derivatives (Me_2SiSiMe_2) [η~5-C_5H_4Fe(CO)_2R]_2[5, R=Me; 6, R=PhCH_2; 7, R=CH_3C(O); 8, R=PhC     

THE STUDY OF SPECTRA AND X-RAY CRYSTAL STRUCTURE OF A NOVEL BIONICS INSECTICIDE——(CH_3)_2NHCH(CH_2S_2O_3)_2Na·H_2O

IR and NMR spectra of novel bionics insecticide—C_5NS_4O_6H_(12)Na·H_2O have been studied. The molecular and crystal structures of the compound also have been determined. The compound crystallizes in the monoclinic space group C_(2h)~5, - P2_1/n with α= 8.0972. (9) , b =16.262(4), c = 10.370(3), β= 94.26(2)° and z = 4.The result shows that N atom in this compound captures a proton to form HN~ group, Na~ is in statistical disorder. Therefore, the structural formula of tho compound is (CH_3)_2HN~ —CH(CH_2S_2O_3~-)_2·1/2 (Na~ )_2·H_2O.