共查询到20条相似文献,搜索用时 619 毫秒
1.
M David Curtis 《应用有机金属化学》1992,6(5):429-436
Sulfido clusters which incorporate molybdenum and a late transition metal, e.g. iron, cobalt or nickel, are readily prepared by the reactions of Cp2Mo2S4, Cp2Mo2S2(SR)2 or Cp2Mo2(CO)2(SR)2 with Fe2(CO)9, Co2(CO)8, Ni(CO)4, Cp2Ni, etc. The homogeneous reactions of the cluster Cp2Mo2Co2S3(CO)4 with thiols, thiophene, and phosphines are reviewed, as are some reactions of the clusters with metal oxide surfaces to produce heterogeneous catalysts for CO hydrogenation or hydrodesulfurization. 相似文献
2.
《Journal of organometallic chemistry》1991,418(2):C24-C27
An X-ray study of [(μ-η2,η3-HCCCH2)Cp2Mo2(CO)4]+(BF4−) (1) and [(μ-η2,η3-HCCCMe2)Cp2Mo2(CO)4]+(BF4−) (2) reveals their structures to be similar to the structure of neutral compounds of the series (μ-η2,η2-RCCR)Cp2Mo2(CO)4, the difference between 1 and 2 being mainly due to the markedly different MoC+ bond lengths, which accounts for different stability and fluxional behavior of these compounds in solution. 相似文献
3.
Mehdi ElsayedMoussa Michael Seidl Gbor Balzs Matthias Hautmann Manfred Scheer 《Angewandte Chemie (International ed. in English)》2019,58(37):12903-12907
The reactions of tetrahedral molybdenum complexes bearing unsubstituted heterodiatomic Group 15 elements, [Cp2Mo2(CO)4(μ,η2:η2‐PE)] (Cp=C5H5; E=As ( 1 ), Sb ( 2 )), with CuI halides afforded seven unprecedented neutral supramolecular assemblies. Depending on the Mo2PE units and the CuI halide, the oligomers [?{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1‐PE}?4?{CuX}{Cu(μ‐X)}?2] (E=As (X=Cl ( 3 ), Br ( 4 )); E=Sb (X=Cl ( 6 ), Br ( 7 ))) or the 1D coordination polymers [{Cp2Mo2(CO)4}{μ4,η2:η2:η1:η1‐PAs}{Cu(μ‐I)}]n ( 5 ) and [{Cp2Mo2(CO)4}{μ4,η2:η2:η2:η1‐PSb}2{Cu(μ‐X)}3]n (X=I ( 8 ), Br ( 9 )) are accessible. These solid‐state aggregates are the first and only examples featuring the organometallic heterodiatomic Mo2PE complexes 1 and 2 as linking moieties. DFT calculations demonstrate that complexes 1 and 2 present a unique class of mixed‐donor ligands coordinating to CuI centers via the P lone pair and the P?E σ‐bond, revealing an unprecedented coordination mode. 相似文献
4.
M. Angeles Alvarez 《Journal of organometallic chemistry》2010,695(1):36-2066
The 30-electron binuclear anion [Mo2Cp2(μ-PCy2)(μ-CO)2]− reacts with the chlorophosphite ClP(OEt)2 or the organotin chlorides Cl2SnPh2 or ClSnPh3 to give compounds of the formula trans-[Mo2Cp2(μ-E)(μ-PCy2)(CO)2], (E = P(OEt)2, SnPh3, SnPh2Cl). In contrast, this anion reacts with the organosilicon chlorides ClSiR3 (R = Ph, Me) to give unstable silyloxycarbyne-bridged complexes [Mo2Cp2(μ-PCy2)(μ-COSiR3)(μ-CO)], which rapidly hydrolyze to give the known hydride [Mo2Cp2(μ-H)(μ-PCy2)(CO)2]. Two main types of products were also observed in the reactions of the title anion with different chlorocomplexes of the transition and post-transition metals. Thus, the reactions with [MCl2Cp2] (M = Ti, Zr) give moisture-sensitive isocarbonyl-bridged complexes of the type [Mo2Cp2(μ-COMClCp2)(μ-PCy2)(μ-CO)]. In contrast, softer metallic electrophiles such as [AuCl(PR3)] (R = iPr, ptol) react with the anion at the dimolybdenum site to form new trimetallic clusters of the formula [AuMo2Cp2(μ-PCy2)(CO)2(PR3)], also retaining a Mo−Mo triple bond. Subsequent reactions of the latter products with the solvate complexes [Au(PR3)(THF)][PF6] give the tetranuclear clusters [Au2Mo2Cp2(μ-PCy2)(CO)2(PR3)2][PF6] (Mo−Mo = 2.5674(3) Å and Au−Au = 2.7832(2) Å when R = iPr). Finally, the reaction of the title anion with HgI2 gives the pentanuclear cluster [Hg{Mo2Cp2(μ-PCy2)(CO)2}2] or the trinuclear cluster [Mo2Cp2(μ-HgI)(μ-PCy2)(CO)2] depending on the stoichiometry being actually used for the reaction. The trinuclear species is only stable in tetrahydrofuran (THF), and decomposes to give a mixture of the dimeric species [Mo2Cp2(μ-HgI)(μ-PCy2)(CO)2]2 along with variable amounts of the known iodide-bridged complex [Mo2Cp2(μ-I)(μ-PCy2)(CO)2]. 相似文献
5.
Henri Brunner Beate Hoffmann Joachim Wachter 《Journal of organometallic chemistry》1983,252(2):C35-C38
The reaction of Cp(CO)2MoMo(CO)2Cp (Cp = η-C5H5) with an excess of carbodiimides RN=C=NR′ results in the substitution of two carbonyl groups to give the new asymmetrically bridged complexes Cp2(CO)2Mo2μ(η1:η2-RN=C=NR′) with Cp2(CO)4Mo2μ(η1:η2-CNR) complexes as by products. 相似文献
6.
Larry N. Lewis 《Journal of organometallic chemistry》1982,234(3):355-365
The photoacoustic spectrum (PAS) was measured in the near IR region (1000 to 2600 nm) for organic compounds (C6H6, C6D6, C7H8, and C6H12) and organometallic compounds (Cp2Fe, Cp2Fe2(CO)4, Cp4Fe4(CO)4, Cp4Fe4S4, C6H6Cr(CO)3, CpCo(C4Ph4) and CpCo(CO)2). Band assignments were made by comparison to the infrared spectra. The bands were assigned as the CH overtone stretch and combinations of CH and other IR fundamentals. These bands provide fingerprint spectra for these compounds. 相似文献
7.
《Journal of organometallic chemistry》1986,299(3):C38-C42
Trifluoromethyl isocyanide adds to the metal—metal triple bond of bis[dicarbonyl(η-pentamethylcyclopentadienyl)molybdenum] forming Mo2Cp2(CO)4(η2-μ-CNCF3) as the first isolated product. Further addition of trifluoromethyl isocyanide at 0°C leads to the formation of [Mo(CO)2(μ-CNCF3)(η-Cp)]2, which according to crystal structure analysis contains two bridging CF3NC ligands. During the isomerization of this compound in dichloromethane solution at room temperature or in the solid state above 110°C molybdenum—molybdenum bond cleavage and carbon—carbon bond formation occurs, leading to Cp(CO)2Mo(μ-F3CNCCNCF3)Mo(CO)2Cp, which contains 1,1,1,6,6,6-hexafluoro-2,5-diaza-2,3,4-hexatriene as bridging ligand. 相似文献
8.
M. David Curtis 《Journal of Cluster Science》1996,7(3):247-262
The author's work on the reactions of Cp2Mo2Co2S3(CO)4 (1) and Cp2Mo2 Co2S4(CO)2 (2) with organosulfur compounds is reviewed. Reaction pathways that lead to C S bond scission are proposed, and the relexance of these results to HDS reactions mer commercial CoMoS catalysts is discussed. 相似文献
9.
Harry Adams Sarah A Morris Jeffrey C Motley 《Journal of organometallic chemistry》2004,689(3):522-527
Transfer of dithiolene ligands from [Ni(S2C2Ph2)2] to the dimolybdenum complex [Mo2(μ-C2R2)(CO)4Cp2] (R=CO2Me, Cp=η-C5H5) affords the first example of a dithiolene alkyne complex, [Mo2(μ-C2R2)(μ-S2C2Ph2)2Cp2], together with [Mo2(μ-SCRCR)(μ-SCPhCPh)Cp2] in which sulfur transfer from dithiolene to alkyne has occurred. 相似文献
10.
The reaction of ammonium heptamolybdate with hydrazine sulfate in an aqueous solution of glycine at room temperature yielded colorless crystals of (NH4)4[(NH3CH2CO)2(Mo8O28)] · 2 H2O. The crystal is monoclinic, space group C2/c (no. 15), a = 17.234 Å, b = 10.6892 Å, c = 18.598 Å, β = 108.280°, V = 3253.2 Å3, Z = 4. The crystal structure contains ammonium cations and isolated octamolybdate(4–) anions, [(NH3CH2CO)2(Mo8O28)]4–, with two zwitterionic glycine molecules as ligands. 相似文献
11.
《Journal of organometallic chemistry》1987,331(1):45-52
Reaction of Cp*2Mo2S4 (Cp* η5C5Me5) with oxygen yields two isomers of Cp*2Mo2OS3 and Cp*2Mo2O2S2, the constitution of which is determined by means of IR, 1H and 95Mo NMR spectroscopy as well as by X-ray diffraction analysis. The sulfur liberated in this reaction is oxidized and incorporated into an unusually coordinated μ,η1-thiosulfate ligand of the compound [Cp*2Mo2(μ,η2-S2)(μ-S)(υ,η1-S2O3)]. The reaction of all of these compounds with (CO)5Cr(THF) and (CH3CN)3Cr(CO)3, respectively, gives clusters either containing a trigonal-bipyramidal Mo2CrS2 or a cubane-like Mo2Cr2OnS4-n skeleton (n = 1,2) with five metal-metal bonds. This reaction enables the straightforward incorporation of oxygen atoms into 62-e heterocubane clusters and thus the investigation of 95Mo chemical shifts of mixed oxo/thio-heterocubanes by means of NMR spectroscopy. 相似文献
12.
Reactions of Cyclostibanes, (RSb)n [R = (Me3Si)2CH, n = 3; Me3CCH2, n = 4, 5] with the Transition Metal Carbonyl Complexes [W(CO)5(thf)], [CpxMn(CO)2(thf)], [CpxCr(CO)3]2, and [Co2(CO)8]; Cpx = MeC5H4 (RSb)3 [R = (Me3Si)2CH] reacts with [W(CO)5(thf)], [CpxMn(CO)2(thf)], or [Co2(CO)8] to give [(RSb)3W(CO)5] ( 1 ), [RSb{Mn(CO)2Cpx}2] ( 2 ) or [RSbCo(CO)3]2 ( 3 ). The reaction of (R′Sb)n (n = 4, 5; R′ = Me3CCH2) with [CpxCr(CO)3]2 leads to [(R′Sb)4{Cr(CO)2Cpx}2] ( 4 ); Cpx = MeC5H4, thf = Tetrahydrofuran. 相似文献
13.
Dorothy H. Gibson Fahim U. Ahmed Kenneth R. Phillips 《Journal of organometallic chemistry》1981,218(3):325-336
Quaternary ammonium borohydrides, used directly or generated in phase transfer reactions, are highly effective reagents for preparing metal carbonyl anions from metal carbonyls [Mo(CO)6, Mn2(CO)10, Re2(CO)10, CO2(CO)8, Fe3(CO)12, Ru3(CO)12 and (η5-C5H5)2Mo2(CO)6] and from some metal carbonyl halides [BrMn(CO)5 and η5-C5H5Mo(CO)3Cl]. Where strongly basic anions would be formed from a halide [BrMn(CO)4PPh3 and η5-C5H5Ru(CO)2Br], the reactions provide efficient syntheses of the corresponding hydrides instead. The anion η5-C5H5Fe(CO)2? is not accessible by these techniques; reaction of η5-C5H5Fe(CO)2Br yields the iron dimer (via the highly nucleophilic anion) and the dimer is unreactive toward Q+BH4?. Reductions of Re2(CO)10 conducted in CH2Cl2 provide Re2(CO)9Cl? in high yield. 相似文献
14.
Allan R. Pinhas Thomas A. Albright Peter Hofmann Roald Hoffmann 《Helvetica chimica acta》1980,63(1):29-49
The impetus for this work was the structure of a trinuclear complex with two carbonyl groups showing incipient triple bridging - Cp2Rh3(CO)4?. Its structure, barrier to rotation of one Rh(CO)2? piece vs. the rest of the molecule, and the nature of the bridging carbonyl interaction are analyzed. Isolobal analogies form an interesting connection between this complex and a bridged isomer of the recently synthesized carbene complexes, Cp2Rh2(CO)2CR2, one isomer of Cp2Rh3(CO)3, and hypothetical carbyne complexes Cp2Rh2(CO)2CH+,?. A general bonding model for Cp2Rh2(μ-CO)2X complexes is constructed. The model, rich in geometrical detail, allows minima for the bridging carbonyl groups bending toward and away from the bonded ligand X. 相似文献
15.
Chemistry of Hydrogen Isocyanide. VIII. Protonation of a ‘Mobile’ Cyano Ligand: cis-[μ-CNH2)Fe2Cp2(CO)3]X (X = Cl, BF4, PF6, I) . Protonation of the terminal cyano ligand in the complex cis-Na[Fe2(CN)Cp2(CO)3] affords the N-diprotonated produkt [Fe2Cp2(CO)3(μ-CNH2)]+ X? (X = Cl, BF4, PF6, I) exclusively; the structure of the chloride has been determined by X-ray analysis. 相似文献
16.
A.E. Sánchez-Peláez M.F. Perpiñán A. Santos 《Journal of organometallic chemistry》1985,296(3):367-375
The reactions of the zerovalent carbonyl complexes Mo(CO)6 and Mo(CO)4(bipy) with a series of uninegative bidentate (X,Y)-donor ligands (X,Y = xanthates, dithiocarbamates, o-aminophenoxide, o-aminothiophenoxide, 2-picolinate and thioacetate) lead to new anionic tetracarbonyl complex anions [Mo0(X,Y)(CO)4]?. These anions, which can be isolated as their tetraphenylphosphonium salts, contain the (X,Y)-ligand as a bidentate group. In the case of (X,Y) = monothioacetate the decarbonylated species [PPh4][MoII(TA)3] is formed. The reacions of the new complexes with allyl bromide and methyl iodide are described. 相似文献
17.
《Journal of organometallic chemistry》1991,418(3):C33-C38
Reaction of the complexes [(CO)3Co(μ-RC2R′)Co(CO)3] (R = R′ = CF3; R = Ph, CF3 and R′ = H) with the MoMo dinuclear derivative [Mo2Cp2(μ-SMe)2(CO)2] leads to cleavage of both CS and CH bonds with the formation of closo-octahedral Mo2CO2C2 clusters stabilised by a μ4-η2-bound alkyne. An X-ray diffraction study has shown that the two Mo2Co faces of the octahedron are capped by triply-bridging sulphur atoms. 相似文献
18.
19.
M. Angeles Alvarez 《Journal of organometallic chemistry》2009,694(24):3864-2066
The 30-electron dimolybdenum anion [Mo2Cp2(μ-PCy2)(μ-CO)2]− reacts at room temperature with allyl chloride to give the unsaturated σ:π-bonded alkenyl derivative trans-[Mo2Cp2(μ-η1:η2-CMeCH2)(μ-PCy2)(CO)2], this requiring a 2,1-hydrogen shift in the allyl moiety probably induced by the unsaturated nature of the dimetal center. In a similar way, the dimolybdenum anion reacts with trans-1-chloro-2-butene (crotyl chloride) to give a mixture of the alkenyl complexes trans-[Mo2Cp2(μ-η1:η2-CEtCH2)(μ-PCy2)(CO)2] and trans-[Mo2Cp2(μ-η1:η2-CMeCHMe)(μ-PCy2)(CO)2] in a 3:2 ratio, which could not be separated by column chromatography. All these alkenyl species exhibit a dynamic behavior in solution (fast on the NMR timescale even at low temperatures) involving alternative π-bonding of the alkenyl ligand to each metal center. In contrast, the title anion reacts with propargyl chloride (ClCH2-CCH) without further rearrangement of the propargyl moiety, to afford the allenyl derivative trans-[Mo2Cp2{μ-η2:η3-CH2CCH)}(μ-PCy2)(CO)2] as the major species. Acryloyl chloride (ClC(O)-CHCH2) also reacts with the title anion to give a mixture of two products, the carbyne complex [Mo2Cp2{μ-COC(O)CHCH2}(μ-PCy2)(μ-CO)] and the vinyl trans-[Mo2Cp2(μ-η1:η2-CHCH2)(μ-PCy2)(CO)2], in a 1:1 ratio. This reaction is a unique case in which a single electrophile can attack both nucleophilic positions in the dimolybdenum anion, these being located at the O(carbonyl) and metal sites, respectively. The formation of the vinyl derivative requires the decarbonylation of a metal-bound acryloyl group, which proved to be an irreversible reaction, since the addition of CO to the above alkenyl complex gave instead the tricarbonyl vinyl derivative cis-[Mo2Cp2(μ-η1:η2-CHCH2)(μ-PCy2)(CO)3]. The structure of this electron-precise complex was confirmed through a single-crystal X-ray diffraction analysis (Mo−Mo = 3.0858(7) Å). 相似文献
20.
《Polyhedron》2001,20(9-10):1107-1113
The reactions of dipropargyl manolate and terephthalate, respectively, with Co2(CO)8 in THF at room temperature gave four new compounds [R(CO2CH2C2H-μ)2][Co2(CO)6]2 (R=CH2, 1a; R=C6H4, 1b) and [(HC2CH2OCO)R(CO2CH2C2H-μ)][Co2(CO)6] (R=CH2, 2a; R=C6H4-1,4-, 2b), and compounds 2a and b reacted with RuCo2(CO)11 to form two new linked clusters [R(CO2CH2C2H-μ)2][Co2(CO)6][RuCo2(CO)9] (R=CH2, 3a; R=C6H4-1,4-, 3b). The treatment of two dipropargyl esters, respectively, with RuCo2(CO)11 afforded another two new clusters [R(CO2CH2C2H-μ)2][RuCo2(CO)9]2 (R=CH2, 4a; R=C6H4-1,4-, 4b). The reactions of dipropargyl manolate, terephalate with Mo2Cp2(CO)4 gave rise to the formation of dinuclear complexes [(HC2CH2OCO)R(CO2CH2C2H-μ)][Mo2Cp2(CO)4] (R=CH2, 5a; R=C6H4-1,4-, 5b), compound 5a reacted with Co2(CO)8 to produce the cluster [CH2(CO2CH2C2H-μ)2][Co2(CO)6][Mo2Cp2(CO)4] 6a. All the new clusters have been characterized by C/H elemental analysis, IR and 1H NMR spectroscopies. The structure of [CH2(CO2CH2C2H-μ)2][Co2(CO)6]2 1a and [p-(HC2CH2OCO)C6H4(CO2CH2C2H-μ)][Co2(CO)6] 2b have been determined by single crystal X-ray diffraction methods. 相似文献