Further studies of M3(μ3-O)(μ-X)3(μ-O2CCH3)3L3 (M=Mo,W) type clusters with nine core electrons

Four new compounds having nine cluster electrons and cores of the types Mo₃OCl₃, Mo₃OBr₃, and W₃OCl₃ are reported. Compound (1) prepared by reduction of [Bu₄N][Mo₃OCl₆(OAc)₃] in THF with metallic zinc, was shown by X-ray crystallography to be Mo₃OCl₄(OAc)₃ (THF)₂ (1). It forms crystals in space groupP2₁ with unit cell dimensionsa=9.472(2) Å,b=13.546(4) Å,c=9.652(2) Å, =101.70(2)°,V=1201(1) Å₃,Z=2. The [Mo₃(₃-O)(-Cl)₃]⁴⁺ core is surrounded by three -O₂CCH₃ anions, one Cl^–, and two THF and has Mo-Mo distances of 2.620(1) Å, 2.613(1) Å, and 2.530(1) Å, with the shortest bond between the two Mo atoms to which the THF molecules are coordinated. Compounds [Bu₄N]₂ [Mo₃OBr₆(O₂CCH₃)₃] · Me₂CO, (2) and [Mo₃OBr₃(O₂CCH₃)₃(PMe₃)₃]₃ · BF₄, (3) are the first two nine-electron Mo₃ species with a [Mo₃(₃-O) Br₃]⁴⁺ core. Both were obtained by zinc reduction of [Mo₃OBr₆(O₂CCH₃)₃]^– in the presence of (NBu₄) Br (2) or PMe₃ and NaBF₄ (3), and each was characterized crystallographically. Compound (2) crystallized in space group Cc with unit cell dimensionsa=25.037(5) Å,b=12.827(2) Å,c=21.484(4) Å, =122.96(1)⁰,V=5790(3) ų,Z=4. While the anion has no crystallographically required symmetry, its virtual symmetry is C_3v . The Mo-Mo distances are 2.619(2) Å, 2.610(3) Å, 2.644(2) Å, with a mean value of 2.624[14] Å. Compound (3) crystallized in space groupP2₁/c with unit cell dimensionsa=10.846(2) Å,b=25.033(5) Å,c=12.641(5) Å, =94.74(2)⁰,V=3420(2) ų,Z=4. The cation occupies a general position but has virtual C_3v symmetry, with Mo-Mo distances of 2.601(2) Å, 2.610(2) Å, 2.627(2) Å, with a mean value of 2.613[14] Å. Thus the anionic and cationic Mo₃ clusters in (2) and (3), respectively, have average Mo-Mo distances that are equal within experimental error. Compound (4), [NEt₄]₂ [W₃OCl₆(O₂CCH₃)₃] is the first 9-electron compound of this type containing tungsten. It was prepared by reduction of [Et₄N][W₃OCl₆(OAc)₃] in benzene with Na/Hg. It crystallized in space groupP2₁2₁2₁ with unit cell dimensionsa=11.076(2) Å,b=14.345(2) Å,c=21.026(3) Å,V=3574(1) ų,Z=4. The anion resides on a general position but has virtual C_3v symmetry, with W-W distances of 2.577(1) Å, 2.612(1) Å, 2.584(1) Å and a mean value of 2.591[15] Å.     

Chemical Synthesis Studies on Pb Zr Alkoxides: A New Pb-Zr Structural Type,Pb3Zr7(μ4-O)4 (μ3-O)4(μ-O2CCH3) 8(μ-OiPr)6(Oi Pr)4

The compound [Pb₃Zr₇(₄-O)₄ (₃-O)₄(O₂CCH₃)₈ (OPrⁱ)₁₀] has been isolated from a reaction mixture containing known Pb-Zr and Pb-Ti complexes and characterised by ²⁰⁷Pb and ¹ H NMR and IR spectroscopy. The compound crystallises in the space group P with a = 13.778(4) Å, b = 21.916(5) Å, c = 27.768(10) Å; = 86.52(3)°, = 87.68(3)°, = 72.72(2)° V 7989(4) ų, Z = 4, R = 0.0973. A Pb-Zr alkoxide complex containing acetylacetone has also been synthesised using PbO as a reagent having the composition [Pb₂Zr₄(O)₂ (OⁱPr)₆(OⁿPr)₈ (acac)₂] allocated on the basis of MW, mass spectral and ¹H NMR data.     

Syntheses and Crystal Structures of Two Trinuclear Iron(Ⅲ) Carboxylate Complexes: [Fe3(μ3-O)(μ-O2CEt)6(H2O)3]Cl.3H2O and [Fe3(μ3-O)(μ-O2CEt)6Py3]Cl(Py=pyridine)

Two new oxo-centered trinuclear iron complexes [Fe3(μ3-O)(μ-O2CEt)6(H2O)3]Cl.3H2O 1 and [Fe3(μ3-O)(μ-O2CEt)6Py3]Cl 2 were prepared in non-aqueous solvent and their crystal structures have been determined. Crystal 1 is monoclinic, space group P21/n, a=9.909(3), b=24.467(8), c=14.542(7)(), β=107.85(4)° V=3356(4)()3, Z=4, Mr=765.52, Dc=1.52 g/cm3, μ=14.28 cm-1, F(000)=1588 and R=0.059, Rw=0.071 for 3745 unique reflections with I>3σ(I). Crystal 2 belongs to the monoclinic system with space group C2/c, a=13.750(3), b=18.439(4), c=16.696(3)(), β=93.42(3)°, V=4226(3)()3, Z=4, Mr=894.73, Dc=1.41 g/cm3, μ=11.4 cm-1, F(000)=2322 and R=0.058, Rw=0.062 for 2272 unique reflections with I>3σ(I). The two structures contain the same trimetal framework in which three iron(Ⅲ) atoms form a nearly equilateral triangle with a μ3-oxygen atom in the centre.     

THE SYNTHESIS AND CRYSTAL STRUCTURE OF Mo_3(μ_3-O)-(μ-S)_3(μ-OOCCH_3)(dtp)_3(Py)

<正> The title compound was obtained by the reaction of Mo3(μ3-O) (μ-S)3(dtp)4(H2O) with CH3COONa and pyridine. Mo3C19H38N1O9P3S9,Mr= 1093. 79, triclinic, space group P1, a = 12. 921(3) , b = 14. 260(3) , c= 12. 800(3)(?),α = 97. 54(2), β=116. 66(1), γ=100. 10(2) °, V = 2015, 2(8)(?)3, Z=2, Dc = 1. 80gcm-3, F(000) = 1092, final R = 0. 066 for 3444 observations, room temp. In the structure the three Mo atoms form an isosceles triangle capped by a μ3-O atom with three sides of 2. 589(2) , 2. 642(2), and 2. 627(2) (?) respectively, and the car-boxyl bridged Mo-Mo bond is the shortest one.     

三核钼簇合物(Me4N)[Mo3(μ3-O)(μ-Cl)3(μ-O2CH)3Cl3]的制备和晶体结构测定

标题簇合物系通过液相氧化低价钼(MoCl3)制得,晶体属正交晶系,空间群为D2h[16]-Pmnb,晶胞参数:α=11.403(1),b=12.345(2),c=14.292(2)A,V=2011.8(8)A[3].Z=4,Dc=2.396g.cm[-3].使用四圆衍射仪收集衍射数据,晶体结构用重原子法解出,经全矩阵最小二乘修正,R=0.050,Rw=0.056.簇阴离子结构属M1型三核钼簇构型,Mo-Mo键2.577A;Mo-O-μ3键1.982A.还讨论了桥原子、键级以及配体对Mo-Mo键的影响。     

STRUCTURAL STUDIES OF THE COPPER(II) ACETATE COMPLEXES Cu(o2CCH3)2(pyridine)3 AND Cu6(μ-O2CCH3)4(μ4-O2CCH3)2(μ-OCMe3)6

Abstract

[Cu(O₂CCH₃)₂]₂, 1, reacts with pyridine to form violet-blue Cu(O₂CCH₃)₂(pyridine)₃, 2, in > 90% yield. 2 crystallizes from pyridine with a distorted square-pyramidal geometry around copper with the monodentate acetate ligands located diagonally in the basal positions. 1 reacts with Bi(OCMe₃)₃ in THF to form blue Cu₆(μ-O₂CCH₃)₄(μ₄-O₂CCH₃)₂(μ-OCMe₃)₆, 3. 3 crystallizes from THF/hexanes with a hexagon of copper atoms linked by six doubly-bridging tert-butoxide ligands, four doubly-bridging bidentate acetates, and two quadruply-bridging bidentate acetate ligands.     

CRYSTAL STRUCTURE AND REACTIVITY OF (Et_4N) [Mo_3(μ_6-O)-(μ-Cl)_3(μ-OAc)_3Cl_3]

<正> (Et4N)[Mo3(μ3-O)(μ-Cl)3(μ-OAc)3Cl3], C14H29Cl6Mo3NO7, Mr = 823.92, triclinic, P1, a = 17. 508(4), b = 19. 602(3), c=8. 091(2)A, α=91. 25(2)°, β= 96. 56(2)°,γ= 83. 61(2)°, V = 2741(1)A3, Z = 4, Dc = 2.00g/cm3, MoKa (λ=0. 71069A), μ= 19. 44cm-1, F(000) = 1616, T = 23℃, final R = 0. 055, Rw = 0. 068 for 5728 unique intensity data (I≥3σ(I)).The molecule consists of cluster aniorn [Mo3(μ3-O) (μ-Cl)3(μ-OAc)3Cl3]- and cation (Et4N) + . There are two independent molecules in an asymmetric unit whose cluster anions A and B have the same configuration except for some bonding parameters. The cluster core may be described as an equilateral {Mo3} triangle with a capping O atom and three bridging Cl atoms below and above it respectively. In addition, each pair of Mo atoms is bridged by an acetate group and each Mo atom is further coordinated to a terminal chlorine atom. The three Mo - Mo bonds are 2. 587 (2), 2.587(2), 2. 582(2) A for cluster anion A and 2. 587(2), 2.595(2), 2.577 (2) A for cluster a     

CRYSTAL STRUCTURE OF (Et_4N)2 [Mo_3 (μ_3-O) (μ_3-Cl) (μ-Cl)_3 Cl_6]·EtOH

<正> Mr=963.9, monoclinic, P21/c, a=11.379(3), b=20.766(2), c=14.487(3) A,β=91.49(2)°, V=3518.9A3, Z=4, Dm=1.81, Dx=1.819 g·cm-3, MoKα radiation, λ=0.71073A, μ=18.167, F(000)=1916, T=293 K, R=0.040 for 3261 reflections. The structure consists of two sets of tetraethylammonium cations and trinuclear Mo cluster anions. The cluster skeleton is formed by three Mo atoms arranged in an isosceles triangle with a Cl and an O atoms as capping ligands.     

SYNTHESIS AND CRYSTAL STRUCTURE OF COMPLEX [CrMo_3 (μ_3-O)_3(μ-O)(μ-O_2CCH_3)_5(O_2CCH_3)_3]Na2 · H_2O

<正> The title complex C CrMo3 (μ3-O )3 (μ-O) (μ-O2CCH3 )5 (O2CCH3)3]2Na2 · H2O (Mr=1814. 32) crystallizes in monoclinic, space group P21/ n with a=11.209(5), b=18. 05(1), c=14. 44(1) A , β= 98. 30(5)°. V=2890 (3) A3, Z=2, A = 2. 08 g/cm3, F(000) -1780, Final R = 0. 049, Rw = 0. 058 for 2622 independent reflectons with I>3σ(I). The complex anion contains two Mo3O4 cores which connect two chromium atoms through four μ3-O atoms and eight bridging CH3COO- groups. Each of the Cr atoms and the Mo atoms is coordinated by six oxygen atoms. The anions are linked by Na cations to form one-dimensional infinite chain structure.     

CRYSTAL STRUCTURE OF Mo_3(μ_3-O) (μ-S_2)_ 3 [S_2P(OEt)_2]_3I

<正> Mr=1178.9, monoclinic, P21/n, a=16.570(2), b=12.370(1), c=20.007(2) A,β=99.97(1)°, V=4039.0A3, Z=4, Dx=1.938 Mgm-3, λ(MoKα)=0.7107A, μ(MoKα)=23.96 F(000)=2296, room temperature. Final R value=0.047 for 4387 unique observed reflections. It consists of neutral mono-oxo-capped trinuclear molybdenum cluster molecules with an average Mo-Mo bond length of 2.626(4)A and an average Mo-0 bond length of 2.036(2)8.     

THE SYNTHESIS AND STRUCTURE OF Mo_3(μ_3-O)(μ-S)_3(μ-O_2CC_6H_5)_2(dtp)_2(Py)

<正> The title compound was prepared by reaction of Mo3(μ3-O) (μ-S)3-(dtp)4 (H2O) with C6H5COONa and pyridine. C27 H35 Mo3NO9P2S7, Mr = 1091.76, monoclinic, space group P21/c, a = 15. 057(5), b = 13. 052(5), c = 21. 662(6)(?), β=105.97(2)°, V = 4093(2) (?)3, Z = 4, Dc= 1. 77gcm-3, F(000) = 2176, μ(MoKα)=13.50cm-1, final R =0. 068 for 2835 observations. The molecular configuration is new and of approximate C, symmetry, and there are two C6H5COO bridging groups in the structure. The three Mo atoms form an isosceles triangle with three sides of 2. 567(3), 2. 576(3), and 2. 649(3)(?), where the two Mo-Mo bonds bridged by C6H5COO group are much shorter than that without. Something about the reactivity of Mo clusters is discussed.     

Syntheses and characterization of the vanadium trimer (V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6(4,4′-bipyridine) and the vanadium hexamer [(V3(μ3-O)O2)(μ2-O2P(CH2C6H5)2)6]2(μ2-N1,N2-di(pyridin-4-yl)oxalamide)

Reacting VO(acac)₂ with six equivalents of dibenzylphosphinic acid in the presence of 4,4′-bipyridine or μ₂-N¹,N²-di(pyridin-4-yl)oxalamide leads to trimeric (V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆(4,4′-bipyridine) or the hexamer [(V₃(μ₃-O)O₂)(μ₂-O₂P(CH₂C₆H₅)₂)₆]₂(μ₂-N¹,N²-di(pyridin-4-yl)oxalamide). The complexes were characterized by spectroscopic (FTIR and ¹H NMR spectroscopies), TGA, and by single crystal X-ray diffraction measurements. The structures consist of a planar central core where three vanadium ions are arranged in the form of a quasi-isosceles triangle and contain an interstitial O which is multiply bonded to one V and weakly interacting at different bond distances to the remaining two V ions.     

Solution and solid state characterization of oxo-centered trinuclear iron(III) acetate complexes [Fe3(μ3-O)(μ-OAc)6(L)3]+

[Fe(3)(μ(3)-O)(μ-OAc)(6)(py)(3)][FeBr(4)](2)[py·H], complex (1), (OAc is acetate) was prepared from the reaction of FeBr(3) with pyridine in 1.2 molar aqueous HBr and 2.4 molar aqueous CH(3)COOH. Recrystallization of 1 in acetonitrile produced the [Fe(3)(μ(3)-O)(μ-OAc)(6)(py)(3)][FeBr(4)] complex (2). Both complexes were characterized by IR and (1)H NMR spectroscopies and their structures were studied using the single-crystal diffraction method. There is a lack of thorough characterization of the titled compounds in solution. Paramagnetic (1)H NMR is introduced as a good probe for the characterization of a family of titled compounds in solution when the L ligand coordinated to iron varies as: CH(3)OH, CH(3)CN, DMSO, H(2)O, py and acetone.     

Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2

The reactions of the heterometallic complexes (-H)Os₃(-O₂CC₅H₄FeCp)(CO)₁₀ (1) and Fe{(-O₂CC₅H₄)(-H)Os₃(CO)₁₀}₂ (2) with CF₃COOH, CF₃SO₃H, and AcCl were studied. The reaction of 1 with CF₃COOH involves interaction with the Cp ligands, protonation of the O atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF₃SO₃H protonates the O atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2with either CF₃COOH or low concentrations of CF₃SO₃H results in successive elimination of two [(-H)Os₃(CO)₁₀] cluster fragments due to protonation of the O atoms of the carboxylate groups. In the case of high CF₃SO₃H concentrations, the Os—Os bonds of both cluster fragments of 2 are also protonated to give the [Fe{(-O₂CC₅H₄)(-H)₂Os₃(CO)₁₀}₂]²⁺ dication. The Friedel—Crafts acylation of 1 takes place only when a large excess of AcCl and AlCl₃ is used to give two new complexes, (-H)Os₃(-O₂CC₅H₄FeC₅H₄C(O)CH₃)(CO)₁₀ and (-H)Os₃(-O₂CC₅H₃C(O)CH₃FeCp)(CO)₁₀ in a 2 : 1 ratio.     

Synthesis and structure of three isomeric cluster complexes (μ-H)Os3μ-O2CC5H4Mn(CO)3(PPh3)2(CO)8

The reaction of (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(CO)₁₀ with PPh₃ in the presence of Me₃NO gave mono- and disubstituted heterometallic complexes (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(PPh₃)(CO)₉ and (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃ (PPh₃)₂(CO)₈. Crystal structure determination was performed for three isomeric cluster complexes (μ-H)Os₃μ-O₂CC₅H₄Mn(CO)₃(PPh₃)₂(CO)₈, which are both geometrical and conformational isomers differing in color. The geometrical isomerism is due to the attachment of the PPh₃ group at different vertices of the Os₃ triangle relative to the O₂CC₅H₄Mn(CO)₃ bridging ligand. The conform ational isomerism implies that the molecules have the same arrangement of ligands and differ only in the values of bond angles between the planar fragments of the clusters.     

The synthesis and crystal structure of novel Mo-Sn tetranuclear cubane-like cluster [Mo3(SnBr3)(μ3-O)(μ3-S)3(dtp)3(py)3]·(CH2Cl2)

The synthesis and crystal structure of the first example for hybrid Sn-Mo tetranuclear cubane-like cluster compound containing S/O mixed triple capping atom [Mo₃(SnBr₃)(μ ₃-O)(μ ₃-S)₃(dtp)₃(py)₃]·(CH₂Cl₂) (A) (dtp=S₂P(OC₂H₅)₂) are reported. The compound is prepared by the reaction of [Mo₃(μ ₃-O)(μ-S)₃(dtp)₄·(H₂O)] with SnBr ₃ ^? . The molecular structure of the cluster can be described as a [Mo₃OS₃] core with the SnBr ₃ ^? fragment linked to {Mo₃} triangle by three (μ ₃-S). Three Mo-Mo bond lengths are 2.616(2), 2.620(2), 2.628(2) Å, respectively, and the molecule has approximately C_3v symmetry. There is no bonding between Sn and Mo atoms, however, the addition of SnBr ₃ ^? may cause electron transfer from Sn²⁺ to [Mo₃OS₃] core to result in the shortening of Mo-Mo bond distances. The compound crystallizes in the monoclinic space group P2₁/n with refined lattice parameters ofa=13.012(4),b=22.877(6),c=18.585(6) Å,β=96.34(3)°,V=5498(3)ų, andZ=4. Full matrix refinement converged with final agreement factor ofR=0.054,R _w=0.064.     

Synthesis and crystal structure of an ionic cluster {[Mo_3(μ_3-O)(μ-S)_3(dtp)_3(py)_3][CdI(dtp)_2]}

A new cluster compound {[Mo3(μ3-O)(μ-S)3(dtp)3(py)3][CdI(dtp)2]} (dtp=S2P(O-was obtained from the reaction of (Mo3OS3(dtp)4(H2O)] with a CdI2-Bu4NI mixture.The molecular structure is composed of a cluster cation [Mo3OS3(dtp)3(py)3]+ and the complex anion [CdI(dtp)2]-Crystal data:Triclinic,space group P1 with cell parameters a=1.4672(7),b=1.5356(5),c=1.6806(5) nm,α=74.59(3),β=67.89(4),7=78.86(3)°,V=3.364(2) nm3,and Z=2,least-squares refinement of 8941 reflections gives a final agreement factor of R=0.052,Rw=0.065.     

Co-complexation of Lithium Gallates on the Titanium Molecular Oxide {[Ti(η(5)-C(5)Me(5))(μ-O)}(3)(μ(3)-CH)

Amide and lithium aryloxide gallates [Li(+){RGaPh(3)}(-)] (R = NMe(2), O-2,6-Me(2)C(6)H(3)) react with the μ(3)-alkylidyne oxoderivative ligand [{Ti(η(5)-C(5)Me(5))(μ-O)}(3)(μ(3)-CH)] (1) to afford the gallium-lithium-titanium cubane complexes [{Ph(3)Ga(μ-R)Li}{Ti(η(5)-C(5)Me(5))(μ-O)}(3)(μ(3)-CH)] [R = NMe(2) (3), O-2,6-Me(2)C(6)H(3) (4)]. The same complexes can be obtained by treatment of the [Ph(3)Ga(μ(3)-O)(3){Ti(η(5)-C(5)Me(5))}(3)(μ(3)-CH)] (2) adduct with the corresponding lithium amide or aryloxide, respectively. Complex 3 evolves with formation of 5 as a solvent-separated ion pair constituted by the lithium dicubane cationic species [Li{(μ(3)-O)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-CH)}(2)](+) together with the anionic [(GaPh(3))(2)(μ-NMe(2))](-) unit. On the other hand, the reaction of 1 with Li(p-MeC(6)H(4)) and GaPh(3) leads to the complex [Li{(μ(3)-O)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-CH)}(2)][GaLi(p-MeC(6)H(4))(2)Ph(3)] (6). X-ray diffraction studies were performed on 1, 2, 4, and 5, while trials to obtain crystals of 6 led to characterization of [Li{(μ(3)-O)(3)Ti(3)(η(5)-C(5)Me(5))(3)(μ(3)-CH)}(2)][PhLi(μ-C(6)H(5))(2)Ga(p-MeC(6)H(4))Ph] 6a.     

Syntheses and Crystal Structures of Two Trinuclear Iron(Ⅲ) Carboxylate Complexes:〔Fe_3(μ_3-O)(μ-O_2CEt)_6(H_2O)_3〕Cl·3H_2O and 〔Fe_3(μ_3-O)(μ-O_2CEt)_6Py_3〕Cl(Py=pyridine)

１ＩＮＴＲＯＤＵＣＴＩＯＮＴｒｉｎｕｃｌｅａｒｏｘｏ ｃｅｎｔｅｒｅｄｍｅｔａｌｃａｒｂｏｘｙｌａｔｅａｓｅｍｂｌｉｅｓｏｆｔｈｅｇｅｎｅｒａｌｃｏｍｐｏｓｉｔｉｏｎ〔Ｍ３（μ３ Ｏ）（μ２ Ｏ２ＣＲ）６（Ｌ）３〕ｎ＋ｈａｖｅｂｅｎｏｆｉｎｔｅｎｓｅ...