Synthesis, molecular structures, and properties of heterometallic cobalt tetramethylcyclobutadiene complexes (C4Me4)Co(CO)2TePh, (C4Me4)Co(CO)2TePh[W(CO)5], and Me4C4Co(μ3-S)2Cr2Cp2(μ-SC4H9)

The reaction of Cb*Co(CO)₂I (1) (Cb* is tetramethylcyclobutadiene) with sodium phenyltelluride afforded the mononuclesar complex Cb*Co(CO)₂TePh (2). The reaction of the latter with W(CO)₅(THF) produced the Cb*Co(CO)₂TePh[W(CO)₅] compound (4). The reaction of 1 with the Cp₂Cr₂(SCMe₃)₂S complex gave the heterometallic cluster Cb*Co(μ₃-S)₂Cr₂Cp2 (μ-SCMe₃) (5). Complexes 2, 4, and 5 are diamagnetic. Their structures were determined by X-ray diffraction. Complex 2 contains the Co-Te bond (2.585(1) Å); complex 4, the Co-Te (2.558(8) Å) and W-Te (2.8467(6) Å) bonds. Complex 5 has the stable triangular sulfide-and tert-butylmercaptide-bridged core Cr₂Co (Cr-Cr and Cr-Co bond lengths are 2.626(2) and 2.673(2) Å, respectively) with Cp ligands at the chromium atoms and a Cb* ligand at the cobalt atom. Complex 5 was characterized by cyclic voltammetry. The thermolysis of complex 4 was studied.     

Synthesis and characterisation of hexanuclear ruthenium clusters containing a μ4-nitrene ligand. Crystal structures of [Ru6(CO)15(μ-CO)2(μ4NH)(μ-OMe)μ3-η2-N(H)C(O)OMe] and [Ru6(CO)16(μ-CO)2(μ4-NH)(μ-OMe)(μ-NCO)]

Two hexaruthenium carbonyl clusters [Ru₆(CO)₁₅(μ-CO)₂(μ₄-NH) (μ-OMe){μ₃-η²-N(H)C(O)OMe}] and [Ru₆(CO)₁₆(μ-CO)₂-(μ₄-NH)(μ-OMe)(μ-NCO)]2 have been isolated from the pyrolysis of H₂Ru₃(CO))₉NOCH₃, and single-crystal X-ray structure analysis shows that both 1 and 2 have a square planar arrangement of four ruthenium atoms capped by a μ₄-nitrene ligand, with two additional ruthenium atoms bridging two opposite RuRu edges of the square base to form a ‘boat’ form metal framework.     

Synthesis,structure, and properties of a new trinuclear iron cluster, [(MeOH)(H2O)2Fe3(μ3-O)(μ-OOCC6H4OCH2C5H4NH)6] (ClO4)7 · · 8MeOH · 3.5H2O

Reactions of iron(m) salts with a new bidentate ligand, which is potentially capable of forming binuclear iron complexes upon complexation, were studied. Under various conditions, we succeeded in isolating only the trinuclear cationic complex (Fe^III ₃(O₂CR)6(₃-)17+ (1), where RCO₂ is 2-(pyrid-2-ylmethoxy)benzoic acid protonated at the pyridyl moiety. The structure of 1 was established by spectral, magnetic, and X-ray structural studies. Cyclic voltammetry in McCN in the temperature range from -35 to 20 °C demonstrated that 1 undergoes successive Fe^IIIFe^II reduction in three one-electron stages, which is indicative of the electronic interaction between iron atoms in the complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2086–2092, August, 1996.     

Formation of mixed-metal alkoxides mediated by the reactivity of coordinated pinacol: Synthesis and molecular structures of Ce2Ti2(μ3-O)2(μ,η2-OCMe2CMe2O)4(OPri)4(PriOH)2 and of Ce2Nb2(μ3-O)2(μ,η2-OCMe2CMe2O)4(OPri)6

The addition of pinacol to mixtures of titanium and cerium isopropoxides as well as the use of insoluble titanium and cerium pinacolate synthons was investigated as a route to M-Ce (M=Ti, Nb) species. Pinacol was able to promote the formation of mixed-metal species and the first Ce-Ti and Ce-Nb species namely Ce_2Ti(pin)₂(OPrⁱ)₈ and [M₂Ce₂(μ₃-O)₂(μ,η²pin)₄(OPrⁱ)₆H_x] [M=Ti, x=2; M=Nb, x=0; pin=OCMe₂-COMe₂] were isolated and characterized by FT-IR and ¹H NMR. The latter were also characterized by X-Ray diffraction. Their structures are based on a rhombus compressed along the M⋯M direction with 6-coordinated metals. The pinacolate moieties act as bridging-chelating ligands. The metal–oxygen bond lengths vary according to M–O(pin)<M-μ₃–O<Mμ–O(pin)<Ce–OPrⁱ<Ce–μ₃O.     

新型TiCl4(Ni(acac)2复合催化剂乙烯聚合反应

乙酰丙酮镍;四氯化钛;四氯化硅;新型TiCl4(Ni(acac)2复合催化剂乙烯聚合反应     

Syntheses and structures of three complexes of formulas [L3Co(μ2-O2P(Bn)2)3CoL'][L"], featuring octahedral and tetrahedral cobalt(II) geometries; variable-temperature magnetic susceptibility measurement and analysis on [(py)3Co(μ2-O2PBn2)3Co(py)][ClO4

The syntheses and structural properties of three dinuclear complexes [L(3)Co(μ(2)-O(2)P(Bn)(2))(3)CoL'][L"] [one ionic L(3) = py(3), L' = py, L" = ClO(4)(-) (1) and two molecular L(3) = py(3), L' = Cl (2) and L(3) = py, μ(2)-NO(3)(-), L' = py (3)] are reported. Complexes feature octahedral Co(II) sites bridged by three dibenzylphosphinate ligands to a tetrahedrally ligated Co(II) site, with the remaining coordination sites occupied by py, nitrato, and Cl ligands. The Co-Co distances are 4.248 ? at 291 K and 4.265 ? at 100 K for 1 and 4.278 and 4.0313(7) ? for 2 and 3, respectively at 100 K. A fit of the low-temperature magnetic susceptibility data was derived for complex 1 with g = 2.25, TIP = 700 × 10(-6) cm(3) mol (-1), λ = -173 cm(-1), κ = 0.93, ν = -3.9, Δ = 630 cm(-1), J = 0.15 cm(-1), and θ = -1.8 resulting in R(χ(M)) = 2.5 × 10(-5) and R(χ(M)T) = 5.8 × 10(-5).     

Synthesis, Characterization and Crystal Structure of [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2]

The reaction of μ-alkyne-bridged dimolybdenum compound [Mo2(μ-C2HPh)(CO)4(η5-C5H4C(O)Me)2] 1 with Co2(CO)8 in refluxing toluene gave a new butterfly compound [Co2Mo2(μ4-C2HPh)(μ-CO)4(CO)4(η5-C5H4C(O)Me)2] 2 which was fully characterized by elemental analysis, IR, 1H NMR and X-ray single crystal diffraction techniques. 2 crystallized in monoclinic system, C30H20Co2Mo2O10, Mr=850.23, space group P21/a(#14), a=14.165(5), b=12.498(2), c=16.204(2)(A), β = 96.50(2)°, V = 2850(1)(A)3, Z = 4, Dc = 1.981 g cm-3, F(000)=1672, μ(MoKα)=20.41 cm-1, final R=0.030, Rw=0.039 for 4831 observable reflections with I>2σ(I). The structure contains a Co2Mo2 butterfly core, and each Mo-Co bond is spanned by an asymmetric semi-bridging carbonyl ligand.     

Acetylene as a ligand on clusters: An accurate determination of the crystal and molecular structure of (Cp)2Ni2Fe(CO)3(μ3−C2H2) and of (CP)2Ni2Fe2(CO)6(μ4−C2H2)

Abstarct The Cp)₂Ni₂Fe(CO)₃(µ₃-C₂H₂) and Cp)₂Ni₂Fe(CO)₃(µ₃-C₂H₂) (B) complexes have been synthesized and spectroscopically characterized. An accurate X-ray study and a comparison with related structures shows that the substituents of the alkyne ligands exert considerable effects on the bonding parameters.Crystal data for complex A, monoclinic space group P2₁/n,a = 8.418(1),b = 15.779(2),c = 14,493(1) Å, = 91.64(1)°,Z = 4, 2753 observed reflections,R = 0.022; crystal data for complex B, monoclinic space group C2/c,a = 16.2189(7),b = 7.445(3),c = 25.745(5) Å, = 103.74(3),Z=8, 1853 observed reflections,R = 0.051.     

Synthesis and Crystal Structure of[Co3(CO)9(μ3-C)C(O)OCH2]2

The title compound [Co3(CO)9(μ3-C)C(O)OCH2]2 was synthesized by the reaction of [Cl3CC(O)OCH2]2 with Co2(CO)8 at 40～50 ℃. Crystal data: C24H4O22Co6, Mr=997.88, monoclinic, space group P21/n(#14), a=9.330(2), b=15.197(4), c=11.783(4), β=91.16(2)°, V=1670.4(7) 3, Z=2, Dc=1.984 g/cm3, μ(MoKα)=30.01 cm-1, F(000)=972.00, T=293K, final R=0.045, Rw=0.051 for 1936 observed reflections with I＞2σ(I). The structure contains two centrosymmetric dimeric molecules in a unit cell, each of which has two tetrahedral skeletons (CCo3) connected through a C(O)OCH3CH2OC(O) bridge.     

Co3(CO)7(μ3-S)(μ,η2-SCNR2)的合成和晶体结构

Co2(CO)8与4个二硫代双(烷基硫代甲酰胺)类前配体[R2NC(S)S]2反应,得4个含烷基硫代甲酰胺基的三核钴羰基硫簇合物.通过元素分析、IR、1H NMR和MS等方法表征了它们的结构,用X射线衍射法测定了其中一个簇合物Co3(CO)7(μ3-S)[μ,η2-SCN(i-Pr)2](Ⅲ)的晶体结构.晶体属单斜晶系,P21/n空间群,晶胞参数a=1.145 2(2)nm,b=1.502 8(3)nm,c=1.2144(2)nm,a=90°,β=92.15(3)°,γ=90°,V=2.088 5(7)nm3,Z=4,F(000)=1 096,Dc=1.747 mg·m-3,GOF(F2)=0.835,μ=2.588 nm-1.最终因子R[I＞2σ(I)]=0.040 7,Rw=0.062 4.     

Synthesis and characterisation of novel selenium-containing clusters; crystal structures of [Ru4(μ4-Se)2(CO)8(μ-CO)3] and [Ru3(μ3-Se)2(CO)7(Ph2P(CH2)3PPh2)]

The compound [Ru₄(μ-Se)₂(CO)₈(μ3-CO)₃] (1), has been obtained in good yield by vacuum pyrolysis of [RU₃(CO)₁₂] with [Ph₂Se₂] at 185°C. Reaction of 1 with 1,3-bis(diphenylphosphino)propane at room temperature affords the novel cluster [RU₃(μ₃-Se)₂(CO)₇(Ph₂P(CH₂)₃PPh₂)] (2). The structures of 1 and 2 have been determined by an X-ray diffraction study.     

Synthesis, Structure, Magnetism and Electrochemical Properties of Linear Pentanuclear Complex: Ni5(μ-dmpzda)4(NCS)2

吡啶修饰的线性五核金属化合物[Ni5(μ-dmpzda)4(NCS)2][ dmpzda-H2=N,N’-Di(4-methyl pyrydin-2-yl)pyrazine-2,6-diamine]被合成并表征,其电化学和磁性被报告。 化合物含有接近180º的 Ni-Ni-Ni角,末端含有两个轴配体的Ni5 线性链。这个五核线性金属链被四个顺式的dmpzda2-配体螺旋包裹。化合物中存在两种类型的Ni-Ni键长：末端连接有轴配体的Ni-Ni键长被配体影响,其键长为2.3821 Å;内部的Ni-Ni距离比较短,为2.2959 Å。两末端的Ni(II)离子由于连接轴配体构成四方锥形(NiN4NCS)并存在较长的Ni-N 键长（2.103 Å),这个键长符合高自旋Ni(II)构型。内部的三个Ni-N 距离为1.886-1.906 Å,这样构成正方形平面(NiN4)并呈低自旋的顺磁构型。化合物显示了同[Ni5(μ-tpda)4(NCS)2]类似的磁性,即在化合物中两末端Ni(II)仍存在反铁磁性的作用。     

Synthesis,Crystal and Molecular Structures of [Co(MH)2(Thio)2][BF4] · H2O and [Co(DH)2(NH3)2][BF4]

Crystal structures of [Co(MH)₂(Thio)₂][BF₄] · H₂O (I) and [Co(DH)₂(NH₃)₂][BF₄] (II), where MH^– is H₃C–C(NOH)–C(NO^–)–H and DH^– is H₃C–C(NOH)–C(NO^–)–CH₃, were determined by X-ray diffraction. The crystals are monoclinic, space group C2/c, unit cell parameters (for I and II, respectively): a = 22.018(2) Å, b = 7.943(1) Å, c = 11.681(1) Å, = 92.68(1)° and a = 21.436(2) Å, b = 6.400(2) Å, c = 12.389(2) Å, = 113.13(1)°. In both cases, the Co(III) coordination polyhedron is a centrosymmetrical trans-octahedron, N₄S₂ for I and N₆ for II. In the crystals of I and II, the complex cations and the outer-sphere [BF₄]^– anions (and the crystal water molecules in I) form elaborate hydrogen bonding system.     

Complexes [Ni2(μ-OH2)(μ-O2CCH(CH3)2)2L2–4((CH3)2CHCO2)2]: Synthesis,Structure, and Mass Spectrometric Studies

Russian Journal of Coordination Chemistry - Three new binuclear aqua-bridged nickel(II) 2-methylpropionate complexes [Ni2(μ-OH2)(μ-O2CCH(CH3)2)2L2–4((CH3)2CHCO2)2] (L is...     

Synthesis, Structure and Properties of a Copper Complex Cu2(μ-PhCOO)2(μ-CH3COO)2(CH3OH)2

The title complex Cu2(μ-PhCOO)2(μ-CH3COO)2(CH3OH)2 1(C20H24Cu2O10, Mr=structure was determined by X-ray diffraction method. Complex 1 belongs to orthorhombic, space group Pbca with a = 13.083(6), b = 8.078(4), c = 21.566(2)(A), V = 2279(2) (A)3, Z = 4, Dc= 1.607g/cm3, F(000) = 1128,μ(MoKa) = 1.918 mm-1, the final R = 0.0506 and wR = 0.1382. Each Cu(Ⅱ)ion is coordinated by five oxygen atoms from two benzoic acids, two acetic acids and one methanol molecule in a slightly distorted square pyramidal environment. The title molecules construct a 2-D complex 1 displays strong emissions. IR and TG-DTA studies are also presented.     

Synthesis,structures, and magnetic properties of a cubane-type cluster [Ni(hmp)(MeOH)Br]4 · 2H2O (hmp−= anion of 2-hydroxymethylpyridine)

[Ni(hmp)(MeOH)Br]₄ ? 2H₂O has been prepared by the reaction of 2-hydroxymethylpyridine with NiBr₂ ? 3H₂O and characterized by IR, elemental analysis, powder X-ray diffraction, thermogravimetric analyses, magnetic measurements, and single crystal X-ray diffraction. The crystal structure shows two independent [Ni(hmp)(MeOH)Br]₄ molecules in the asymmetric unit and [Ni₄O₄]⁴⁺ cubane-type cores. Each octahedral Ni(II) is bridged by four μ₃-CH₂O ^? fragments from four hmp ^? ligands. Magnetic studies show that ferromagnetic coupling gives an S = 4 ground state with significant magnetoanisotropy, and the parameters are J ₁ = 8.56, J ₂ = 2.28, D = ?0.65 cm^?1, and g ≈ 2.13.     

Coordination Compounds of Strontium: Syntheses,Characterizations, and Crystal Structures of [Sr(μ-ONc)2(HONc)4]2 and Sr5(μ4-O)(μ3-ONep)4(μ-ONep)4(HONep)(solv)4 (ONc = O2CCH2CMe3; Nep = CH2CMe3; solv = Tetrahydrofuran or 1-Methyl-Imidazole)

Abstract

We have synthesized and characterized two novel Sr compounds: [Sr(μ-ONc)₂(HONc)₄]₂ (1, ONc ? O₂CCH₂CMe₃), and Sr₅(μ_?O)(μ₃?ONep)₄(μ?ONep)₄(HONep)(solv)₄ [ONep ? OCH₂CMe₃, solv = tetrahydrofuran (THF), 2a; 1-methyl-imidazole (Melm), 2b], that demonstrate increased solubility in comparison to the commercially available Sr precursors. The two metal centers of 1 share four unidentate bridging μ-ONc ligands and complete their octahedral geometry through coordination of four monodentate terminal HONc ligands. The structural arrangement of the central core of 2a and 2b are identical, wherein four octahedral Sr atoms are arranged in a square geometry around a μ₄-O ligand. An additional seven-coordinated Sr atom sits directly atop the μ₄-O to form a square-pyramidal arrangement of the Sr atoms, but the apical Sr-O distance is too long to be considered a bond. In solution, compound 1 is disrupted forming a monomer but 2a and 2b retain their structures.