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1.
A novel mixed‐tribridged dimolybdenum(I) compound [Bn4N][Mo2(μ‐SPh)2(μ‐Cl)(CO)6] (1) has been synthesized from the reaction of Mo2(CO)3(SPh)2 with BU4NCl. Compound 1 was characterized by IR, UV‐Vis and 1H, 13C, 95Mo NMR spectroscopic analyses. The electrochemical behavior was measured by cyclic voltammetry, indicating a quasi‐reversible two‐electron transfer in one step. The crystal structure determined by X‐ray crystallography shows that 1 contains a [Mo2(μ‐S)2(μ‐Cl)]? core with a planar Mo2S2unit and a Cl bridge. The Mo? Mo distance is 0.28709(7) nm, and the Mo‐Cl‐Mo angle is 66.44(4)°. A newface‐sharing bioctahedral structure is discussed.  相似文献   

2.
The novel oxothiomolybdate Mn2(tren)3[Mo2O2S6]2·1.3H2O [tren = tris(2-aminoethyl)amine], synthesized under solvothermal conditions, consists of one-dimensional novel [Mn2(tren)3] n 4+ chains and discrete [Mo2O2S6]2– anions. There are two crystallographically independent chains and four [Mo2O2S6]2– anions in the asymmetric unit. Each Mn atom in the cationic chains is sixfold coordinated by N atoms of the chelating tren molecules. Two of the four crystallographically independent Mn atoms are tridentately coordinated by two tren molecules, whereas the other two are coordinated tetradentately by one tren molecule and monodentately by the remaining primary amino groups from the tren molecules that act as tridentate ligands. The tren ligand bonding modes lead to the formation of the polymeric [Mn2(tren)3] n 4+ chain. One of the four Mn atoms is in the unusual trigonal prismatic coordination state with six surrounding N atoms.  相似文献   

3.
IR and Raman spectra of [Mo2O2S2(S2)2]2- were reported. The resonance Raman spectra and the depolarization ratios in CH3CN solution were measured. By using the data of crystal structure, the simplified normal coordinate calculation of the stretching vibrations for anion [Mo2O2S2(S2)2]2- was performed. The results obtained are useful to assign the vibrational bands of some Mo-Fe-S clusters.  相似文献   

4.
《Polyhedron》1999,18(26):3411-3416
The heterometallic polymeric cluster complexes Na2Ga2[Mo3O4(O2CEt)8]2 (1) and Na2AlGa[Mo3O4(O2CEt)8]2 (2) have been prepared by reaction of Mo(CO)6, NaMoO4·2H2O with GaCl3 and a mixture of AlCl3 and GaCl3 (1:1 molar ratio), respectively, in heated propionic anhydride and characterized by X-ray crystallography. The structures are isostructural and each consists of two triangular propionate cluster units [Mo3O4(O2CEt)8]4−, which act as polydentate ligands to link trivalent heterometal and sodium ions forming one-dimensional chain structures. Both clusters decompose in 2 M HCl at room temperature to produce discrete [Mo3O4]4+ cluster units. Thermal analysis of 1 reveals that the complex is air stable up to 250°C. IR spectra show the characteristic bands of [Mo3O4]4+ cores at 745–812 cm−1.  相似文献   

5.
Iron nitrosyl complexes with general formula [Q4N]2[Fe2(S2O3)2(NO)4] (Q = Me, Et, n-Pr, n-Bu) were synthesized by the exchange reaction of K2[Fe2(S2O3)2(NO)4] with tetraalkylammonium bromides. The molecular and crystal structure of [(CH3)4N]2[Fe2(S2O3)2(NO)4] were studied by X-ray diffraction analysis. The iron atom in the four-membered cycle of the [2Fe–2S] anion is bound to another Fe atom and to two sulfur atoms and is coordinated by two nonequivalent NO groups, each bridging sulfur atom being bound to the SO3group. The structurally equivalent iron atoms are in the state Fe1–(S= 1/2). The Mössbauer spectroscopy method shows that the complexes are diamagnetic due to the strong Fe–Fe bond. It is found that the SO3group provides higher stability of the thiosulfate anion than the anion in Roussin's red salt [Fe2S2(NO)4]2–.  相似文献   

6.
The carbamoyl complex [C(NMe2)3][(CO)4Fe{C(O)NMe2}] ( 1 ) reacts with InMe3 under loss of the methyl groups to produce a variety of compounds from which only the anionic cluster complexes [C(NMe2)3]3[Fe2(CO)6(μ‐CO){μ‐InFe(CO)4(μ‐O2CNMe2)InFe(CO)4}] ([C N 3]3[ 2 ]) and [C(NMe2)3]2[{(CO)4Fe}2In(O2CNMe2)]·THF ([C N 3]2[ 3 ]·THF) could be crystallized and characterized by X‐ray analyses. The anion [ 2 ]3? has a Fe2(CO)9‐like structure and both anions contain the carbaminato ligand either in a bridging or in a chelating function.  相似文献   

7.
The novel polyoxothioanion [Mo4S4O4(OH)2(OH2)3pba]2? where pba4? ligand is the 1,3-propylenebis(oxamate), was prepared by reacting Mo12S12O12(OH)12(OH2)6 ring with [Cu-pba]2? in aqueous medium. NaK[Mo4O4(μ-S)4(μ-OH)2(μ-H2O)(H2O)2(pba)] ·7H2O was isolated in the solid state and fully characterized by X-ray diffraction study (tetragonal, P4(2)/m [a=20.4962(4) Å; b=20.4962(4) Å; c=14.7013(5) Å). The molecular structure consists of an arc cycle shape tetranuclear enchainment {Mo4S4O4(OH)2 (OH2)3} closed by a pba4? ligand. The 3-D packing, resulting from the connection between K+ and Na+ and the coordination complex {Mo4-pba]2? is described. The 1H-NMR characterization of the complex in aqueous solution is given. The 1H-NMR spectrum exhibits four signals assigned to four enantiotopic protons of the alkyl chain of the pba4? ligand and is in agreement with crystal structure of the complex [Mo4-pba]2?. The compound was also characterized by infrared spectroscopy.  相似文献   

8.
In the presence of N, N′‐dicyclohexylcarbodiimide (DCC), (Bu4N)2[Mo6O18(NAr)] ( 1 ) and (Bu4N)2[Mo6O17(NAr)2] ( 2 ), Ar = o‐CH3C6H4, have been synthesized via the reaction of [α‐Mo8O26]4— with o‐toluidine. If the hydrochloride salt of o‐toluidine was added into the reactive mixture, only the monofunctionalized imido derivative of [Mo6O19]2— was obtained; the bifunctionalized derivative of [Mo6O19]2— was exclusively synthesized in the presence of non‐protonated o‐toluidine. The molecular and crystal structures of the hybrid compounds 1 and 2 were determined by X‐ray single crystal diffraction, and their UV, IR and NMR spectra were compared. Additionally, a possible reaction mechanism was proposed.  相似文献   

9.
Thiocomplexes of Molybdenum. Crystal Structure of a Mixed Single Crystal (PPh3Me)2[Mo2Br6(NO)4]/(PPh3Me)2[Mo2Br6S2(NO)2] The reactions of (PPh4)2MoS4 with MoBr4 and MoBr2(NO)2 resp. lead to the binuclear complexes (PPh4)2[S2MoS2MoBr3(SMe2)] and (PPh4)[S2MoS2MoBr2(NO)2], in which the molybdenum atoms are linked by sulfido bridges. The preparation of (PPh3Me)2S6 and (AsPh4)2S7 from Na2S4 and PPh3MeBr, and AsPh4Cl, respectively, in ethanol solution is described. Disulfido briges are a feature of (AsPh4)2[Mo2Br6(S2)2(SMe2)2], which is obtained from MoBr4(SMe2)2 and (AsPh4)2S7. Mixed single crystals containing 2/3 (PPh3Me)2[Mo2Br6(NO)4] and 1/3 (PPh3Me)2[Mo2Br6S2(NO)2] are formed in the reaction of MoBr2(NO)2 with (PPh3Me)2S6, as shown by X-ray single crystal structure determination. The compound crystallizes monoclinic in the space group C2/c (Internat. Tab. Nr. 15) with four formula units per unit cell (2351 independent observed reflexions, Rw = 0.037). The cell parameters are a = 1603 pm, b = 1549 pm, c = 1863 pm; β = 92.2°. The complexes consist of PPh3Me cations and the dimeric anions [Mo2Br6(NO)4]2? and [Mo2Br6S2(NO)2]2? which occur in the ratio 2:1. In these the molybdenum atoms are connected via MoBr2Mo bridges of slightly different lengths (Mo? Br 265 pm and 267 pm) forming a controsymmetric double octahedron. All molybdenum atoms have two terminal bromo ligands with Mo? Br bond lengths of 258 pm and 260 pm; in the [Mo2Br6(NO)4]2? ion each molybdenum has two covalently bonded nitrosyl groups on cis-position with Mo? N bond lengths of 183 pm. In the [Mo2Br6S2(NO)2]2? ion one of the two nitrosyl groups at each metal atom is substituted by a terminal sulfido ligand with a Mo? S bond length of 240 pm. The i.r. spectra are reported.  相似文献   

10.
The tetrapropylammonium (Pr4N+) salt of [(SeO3)2(P2O7)Mo30O90]8? was prepared from a 75 mM MoVI–2.8 mM P2O74?–5.6 mM SeO32?–0.95 M HCl–60% (v/v) CH3CN system, where [(P2O7)Mo18O54]4? and [H6(SeO3)2Mo15O48]4? are first formed, then being spontaneously fused into [(SeO3)2(P2O7)Mo30O90]8?. The [(SeO3)2(P2O7)Mo30O90]8? anion may be isotypic with [(HPO3)2(P2O7)Mo30O90]8?, in which each side of a (P2O7)Mo12O42 fragment is capped by a B-type (HPO3)Mo9O24 unit derived from [H6(HPO3)2Mo15O48]4?. [(XO3)2(P2O7)Mo30O90]8? (X = HP, Se) have the same type of 30-molybdo framework as [(P2O7)2Mo30O90]8?, previously isolated by Koltz. These three 30-molybdo complexes with the same ionic charge of ?8 constitute a new class of polyoxometallates and have common properties of undergoing a two-electron reduction in the absence of H+.  相似文献   

11.
[Mo3S(S2)3(dtc)3]I, [Mo3S(SeS)3(dtc)3](dtc), and [Mo3Se(Se2)3(dtc)3](dtc) (dtc = N,N-diethyldithiocarbamate) were investigated by liquid SIMS-FTMS. The fragmentation pathways were essentially the same for the three compounds and can be explained by two types of fragmentation processes: stepwise abstraction of S/Se atoms as exemplified by the series [Mo3Xz(dtc)3]+ (4 ? z ? 7, X = S, Se), and ligand dissociation, as indicated by the generation of [Mo3Xz(dtc)2]+ (5 ? z ? 7, X = S, Se). The exclusive elimination of the Se-atoms from [Mo3S(Sax-Seeq)3(dtc)3]+ confirmed the inequivalent reactivity of the bridging atoms in axial and equatorial position as observed in previous studies. Collision-induced decomposition (CID) of [Mo3S7(dtc)3]+ ( 1 ), [Mo3S6(dtc)3]+ ( 2 ), [Mo3S(Sax–Seeq)3(dtc)3]+ ( 3 ), and [Mo3Se7(dtc)3]+ ( 4 ) revealed distinctly different fragmentation reactions for the SIMS and CID mode. CID of 1, 3 , and 4 resulted in a two-step reaction with the exclusive elimination of diatomic molecules XY (X,Y = S/Se). In the case of 3 , the selective elimination of Se2 indicated the abstraction of two Se-atoms located in equatorial positions of two different bridging groups. This result is discussed in terms of mechanisms, based on labile M? Xeq and inert M? Xax bonds with an intramolecular formation of a X4 fragment prior to the elimination of X2.  相似文献   

12.
MoO42? is reduced by diethyldithiocarbamate (Et2dtc?) on prolonged digestion in aqueous medium whereby the complex [Mo2VO2S2(Et2dtc)2] is formed. The central moiety Mo2O2S22+ has a high formation tendency. When [Mo2V(S2)6]2? is refluxed with Et2dtc? in ethanol, [Mo2VS (Et2dtc)2] is formed, the X-ray crystal structure of which has been determined (space group P212121, a = 10.550(2) Å, b = 13.820(5) Å, c = 14.723(12) Å, dc = 1.90 g · cm3?, Z = 4). The Mo? Mo distance of the diamagnetic compound is 2.817(2) Å and the average Mo=St distance 2.099(4) Å.  相似文献   

13.
Oxidative addition of diphenyl disulfide to the coordinatively unsaturated [Mn(CO)5]? led to the formation of low-spin, six-coordinate cis-[Mn(CO)4(SPh)2]?. The complex cis-[PPN][Mn(CO)4(SPh)2] crystallized in monoclinic space group P21/c with a = 9.965(2) Å, b = 24.604(5) Å, c = 19.291(4) Å, β = 100.05(2)°, V = 4657(2)Å3, and Z = 4; final R = 0.036 and Rw = 0.039. Thermal transformation of cis-[Mn(CO)4(SPh)2]? to [(CO)3Mn(μ-SPh)3Mn(CO)3]? was completed overnight in THF at room temperature. Additionally, reaction of [Mn(CO)5]? and PhSH in 1:2 mole ratio also led to cis-[PPN](Mn(CO)4(SPh)2]. Presumably, oxidative addition of PhSH to [Mn(CO)4]? was followed by a Lewis acid-base reaction to form cis-[Mn(CO)4(SPh)2]? with evolution of H2.  相似文献   

14.
The tetranuclear compound [Mo2(O2C‐tBu)3]2(μ‐C2O4) ( 1 ) that is prepared from [Mo2(O2C‐tBu)3]4 and oxalic acid, was reacted with MnI2 · 2THF to form the polyoxomolybdate compound [Mn(CH3OH)6] [Mo8O16(OCH3)8(C2O4)] ( 2 ) in a complex redox reaction. Crystals of 2 were analyzed by single‐crystal X‐ray diffraction showing a octanuclear polyoxomolybdate dianion in which the Mo=O moieties are alternately connected through μ‐oxo and μ‐methoxo units. Charge balance in 2 is realized by a manganese(II) cation that is octahedrally coordinated by methanol ligands. The crystal structure is dominated by strong hydrogen bond interactions of the O–H ··· O type of methanol molecules coordinated to manganese as well as additional methanol molecules in the crystal lattice.  相似文献   

15.
New Coordination Motives at Cyclothiazeno Complexes of Molybdenum and Tungsten. Crystal Structures of [{Mo(N3S2)(Cl)(OtBu)2}{Mo(O)(N3S2)(OtBu)}]2 and [W(N3S2)2(LiCl){N≡W(NPPh3)3}2] The metalla cyclothiazeno complexes (Cyclo-1λ6-metalla-3,5-dithia-2,4,6-triazino complexes) [{Mo(N3S2)(Cl) · (OtBu)2}{Mo(O)(N3S2)(OtBu)}]2 ( 1 ) and [W(N3S2)2(LiCl) · {N≡W(NPPh3)3}2] ( 2 ) are formed from [MoCl3(N3S2)]2 and LiOtBu in toluene, and from [WCl3(N3S2)]2 and LiNPPh3 in THF, respectively. The complexes form moisture sensitive, black ( 1 ) or brown ( 2 ) crystals, which we characterized by crystal structure analyses. 1 · Toluene: Space group P 1, Z = 1, lattice dimensions at –83 °C: a = 934.2(1), b = 964.4(1), c = 1700.3(1) pm; α = 83.54(1)°, β = 78.35(1)°, γ = 71.56(1)°, R1 = 0.0339. 2 · 1.625 Toluene · 0.75 THF: Space group P 1, Z = 4, lattice dimensions at –80 °C: a = 1313.8(1), b = 2896.8(2), c = 3384.9(3) pm; α = 82.42(1)°, β = 88.71(1)°, γ = 77.28(1)°, R1 = 0.0603.  相似文献   

16.
On Thallium(I)-oxochloromolybdates: Synthesis and Crystal Structures of Tl[MoOCl4(NCCH3)], Tl[Mo2O2Cl7], and Tl2[Mo4O4Cl14] and the Structure of Tl2[MoCl6] Black crystals of Tl2[MoCl6] are formed in the reaction of TlCl with MoOCl3 in a sealed evacuated glass ampoule at 350 °C. The crystal structure analysis shows that Tl2[MoCl6] (cubic, Fm m, a = 986.35(7) pm) adopts the K2[PtCl6] structure with a Mo–Cl bond length of 236.6 pm. Tl[MoOCl4(NCCH3)] was obtained by the reaction of TlCl with MoOCl3 in acetonitrile in form of yellow, moisture sensitive crystals. The structure (orthorhombic, Cmcm, a = 746.0(1), b = 1463.8(3), c = 857.3(2) pm) is built of Tl+ cations and octahedral [MoOCl4(NCCH3)] anions in which the acetonitrile ligand is bound in trans position to the oxygen. The reaction of TlCl and MoOCl3 in dichloromethane yields Tl[Mo2O2Cl7] and Tl2[Mo4O4Cl14] as green moisture sensitive crystals. The structure of Tl[Mo2O2Cl7] (orthorhombic, Pmmn, a = 694.3(1), b = 951.9(2), c = 904.7(1) pm) consists of Tl+ cations and dinuclear [Mo2O2Cl7] anions, with two equidistant chlorine bridges of 248.2 and one longer chlorine bridge of 265.7 pm. The oxygen atoms are located in the trans positions of the longer chloro bridge. The structure of Tl2[Mo4O4Cl14] (triclinic, P1¯, a = 692.8(1), b = 919.6(1), c = 998.9(1) pm, α = 104.94(1)°, β = 90.31(1)°, γ = 108.14(1)°) is build of Tl+ cations and [Mo4O4Cl14]2– anions which form tetramers of distorted octahedral, edgesharing (MoOCl5) units with chlorine atoms in the bridging positions. The oxygen atoms are located in the trans positions of the longest chlorine bridges.  相似文献   

17.
The electronic structures of the five members of the electron transfer series [Mo(bpy)3]n (n=3+, 2+, 1+, 0, 1?) are determined through a combination of techniques: electro‐ and magnetochemistry, UV/Vis and EPR spectroscopies, and X‐ray crystallography. The mono‐ and dication are prepared and isolated as PF6 salts for the first time. It is shown that all species contain a central MoIII ion (4d3). The successive one‐electron reductions/oxidations within the series are all ligand‐based, involving neutral (bpy0), the π‐radical anion (bpy.)1?, and the diamagnetic dianion (bpy2?)2?: [MoIII(bpy0)3]3+ (S=3/2), [MoIII(bpy.)(bpy0)2]2+ (S=1), [MoIII(bpy.)2(bpy0)]1+ (S=1/2), [MoIII(bpy.)3] (S=0), and [MoIII(bpy.)2(bpy2?)]1? (S=1/2). The previously described diamagnetic dication “[MoII(bpy0)3](BF4)2” is proposed to be a diamagnetic dinuclear species [{Mo(bpy)3}22‐O)](BF4)4. Two new polynuclear complexes are prepared and structurally characterized: [{MoIIICl(Mebpy0)2}22‐O)]Cl2 and [{MoIV(tpy.)2}22‐MoVIO4)](PF6)2?4 MeCN.  相似文献   

18.
Preparation of trans-[Mo6Cl8]Cl4Br22? Starting from Crystalline [Mo6Cl8]Cl4(H2O)2 and Crystal Structure of [(C6H5)4As]2[Mo6Cl8]Cl4Br2 The synthesis of the title compound is successful if the crystallized [(Mo6Cl8)Cl4(H2O)2] containing the H2O molecules in trans-position reacts with HBr + [(C6H5)4As]Br in ethanol in a heterogeneous reaction. The X-ray structure investigation confirms the existence of discrete trans-Br-substituted cluster anions of composition [(Mo6Cl8)Cl4Br2]2? in the crystal. The reaction in homogeneous solutions proceeds to Br-enriched compounds. [(C6H5)4As]2[(Mo6Cl8)Cl4Br2] crystallizes in the triclinic space group P¯1 with a = 11.071(2), b = 11.418(2), c = 12.813(2) Å, α = 116.10(2), β = 95.27(2) and γ = 94.41(2)° (?133°C). The crystal structure at ?133°C was determined from single crystal X-ray diffraction data (R1 = 0.026). The [(Mo6Cl8)Cl4Br2]2?-anions are not completely ordered but distributed statistically among the three positions which are possible within the limits of the ordered [Mo6Cl8]-cores (ratio 11:5:4). The frameworks of the anions consist of Mo6 cluster units with (slightly distorted) octahedral arrangement of the metal atoms (d(Mo? Mo): 2.600(1) up to 2.614(1) Å), which are coordinated by the halogeno ligands in a square-pyramidal manner. The details of the structure will be discussed and compared with similar [(Mo6X8)Y4] cluster units (X, Y ? Cl, Br).  相似文献   

19.
Bis(disulfido)bridged NbIV cluster oxalate complexes [Nb2(S2)2(C2O4)4]4– were prepared by ligand substitution reaction from the aqua ion [Nb2(μ‐S2)2(H2O)8]4+ and isolated as K4[Nb2(S2)2(C2O4)4] · 6 H2O ( 1 ), (NH4)6[Nb2(S2)2(C2O4)4](C2O4) ( 2 ) and Cs4[Nb2(S2)2(C2O4)4] · 4 H2O ( 3 ). The crystal structures of 1 and 2 were determined. The crystals of 1 belong to the space group P1, a = 720.94(7) pm, b = 983.64(10) pm, c = 1071.45(10) pm, α = 109.812(1)°, β = 91.586(2)°, γ = 105.257(2)°. The crystals of 2 are monoclinic, space group C2/c, a = 1567.9(2) pm, b = 1906.6(3) pm, c = 3000.9(4) pm, β = 95.502(2)°. The packing in 2 shows alternating layers of cluster anions and of ammonium/uncoordinated oxalates perpendicular to the [1 0 1] direction. Vibration spectra, electrochemistry and thermogravimetric properties of the complexes are also discussed.  相似文献   

20.
Wang  Shutao  Wang  Enbo  Hou  Yu  Li  Yangguang  Wang  Li  Yuan  Mei  Hu  Changwen 《Transition Metal Chemistry》2003,28(6):616-620
A novel organic/inorganic hybrid molybdenum phosphate, [NH3(CH2CH2)2NH3]3[NH3(CH2CH2)2NH2]Na5-[Mo6O12(OH)3(PO4)(HPO4)3]2·4H2O (1), involving molybdenum presented in V oxidation, has been hydrothermally prepared and characterized by elemental analysis, i.r., u.v.–vis., x.p.s., t.g. and single crystal X-ray diffraction. The structure of the title compound (1) may be considered to consist of two [Mo6O12(OH)3(PO4)(HPO4)3] units bonded together with NaO6 octahedra, forming dimers. Further, these dimers connect with each other through four Na+ cations as bridges, giving rise to novel one-dimensional chain-like skeleton. Piperazines exist among inorganic chains acting as charge balancing cations.  相似文献   

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