Fe3(CO)8(C6H5NC)(μ3-S)2的合成和晶体结构

The title compound Fe_3(CO)_8(C_6H_5NC)(μ_3-S)_2 (Ⅰ) was synthesized by the reaction of C_6H_5NCS with Fe_3(CO)_12 at room temperature. The crystal and molecular structure of the title compound were determined by single ctystal diffraction method. Crystal data: monoclinic, space group P2_1/C, a=12.718(4)Å, b=26.164(10) Å, c=l3.741(7) Å, β=117.18(2) °, V=4067(2) Å3, Z=8, Dc=1.825 g/cm3. The structure was solved by direct method and difference Fourier synthesis, and refined by full-matrix Least-squares with anisotropic thermal paramaters, using 1990 observed reflections [Ⅰ＞3σ(Ⅰ)].The final residual factor was R＝0.076, Rw＝0.082. The substituted ligand (C_6H_5NC)in Fe_3(CO)_8(C_6H_5NC)(μ_3-S)_2 is connected to the Fe(3) atom of the distorted tetragonal pyramid Fe_3S_2 framework.     

Synthesis and characterization of platinum(II) and (IV) complexes containing hexamethyleneimine ligand: crystal structure of [Pt(hexamethyleneimine)2(cyclobutanedicarboxylato)]·H2O

A series of new platinum(II) and platinum(IV) complexes of the type [Pt^II(HMI)₂X] (where HMI=hexamethyleneimine, X=dichloro, sulfato, 1,1-cyclobutanedicarboxylato [CBDCA], oxalato, methylmalonato, or tatronato) and [Pt^IV(HMI)₂Y₂Cl₂] (where Y=hydroxo, acetato, or chloro) were synthesized and characterized by infrared (IR) spectroscopy, ¹³C and ¹⁹⁵Pt nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. Among the complexes synthesized, [Pt^II(hexamethyleneimine)₂(1,1-cyclobutanedicarboxylato)]·H₂O was examined by single-crystal X-ray diffraction. The slightly distorted square planar coordination environment of the platinum metal includes the amino group of the hexamethyleneimine (HMI) molecule and the oxygen atoms of the carboxylato ligand. The cyclobutanedicarboxylic acid (CBDCA) molecule adopts six-member chelating rings with platinum. Hydrogen bonding plays an important part in holding the crystal lattice together.     

FeCo2(CO)7(μ3-S)(O[P(SCH2)2]2)的合成与晶体结构

许多化学工作者对单齿膦配体（ＰＰｈ３,ＰＢｕｎ３,ＰＥｔ２Ｐｈ,Ｐ（ＯＥｔ）３,Ｐ（ＯＣ６Ｈ５）３）与母体簇合物ＦｅＣｏ２（ＣＯ）９（μ３－Ｓ）的取代反应进行过详细研究［１－３］,但对双齿膦配体与母体簇合物的取代反应研究报导较少．Ａｉｍｅ［４］合成了含双齿膦配体的簇合物ＦｅＣｏ２（ＣＯ）７（μ３－Ｓ）（Ｐｈ２ＰＣＨ２ＰＰｈ２）,并用１３ＣＮＭＲ和ＩＲ光谱方法对其结构进行了表征．到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导．ＲｏｓａｎｎａＲｏｓｓｅｔｔｉ［２］通过研究母体簇合物与…     

Synthesis and structure of a novel complex [LCo(OH)2(HCO3)CoL]2[(NC)5Cr(CN)Cr(CN)2].4H2O

A novel complex containing a (μ-bicarbonato)-bis(μ-hydroxo)dicobalt(II) cation and a (μ-cyano)dichromium(III) anion has been obtained and characterized by single crystal X-ray diffraction. The cations have a confacial bioctahedral structure and the anion contains an octahedral Cr(CN)₆³⁻ unit bridging to the second Cr which has trigomal planar geometry.     

Solvothermal synthesis of three new dimeric thiogermanates (enH)4Ge2S6, [Mn(en)3]2Ge2S6 and [Ni(en)3]2Ge2S6 from germanium dioxide and sulfur powder

Three new thiogermanates (enH)₄Ge₂S₆ (1) and [M(en)₃]₂Ge₂S₆ (M=Mn (2), Ni (3); en=ethylenediamine) were synthesized using GeO₂ and S₈ as starting materials in molar ratio of 1:0.5 under solvothermal conditions. These compounds suggest that the dimeric [Ge₂S₆]⁴⁻ anion is likely to be the main germanium-containing species in en system and it also might be preferred as counter anions by the transition metal complex cations in crystallization. The cations of [Mn(en)₃]²⁺ and [Ni(en)₃]²⁺ are even better mineralizers than the protonated amine of [enH]⁺. The crystal systems of [Ge₂S₆]⁴⁻ compounds are related to entities of cations and intermolecular reactions between cations and [Ge₂S₆]⁴⁻ anions. The compounds remove ethylenediamine and H₂S molecules in multi steps when being heated under nitrogen stream.     

Structural characterisation of [Pt(NH3)4]2[W(CN)8][NO3]·2H2O donor–acceptor complex

The bimetallic [Pt(NH₃)₄]₂[W(CN)₈][NO₃]·2H₂O is characterised by single-crystal X-ray diffraction [S.G.P2₁/m(11), a=8.0418(7), b=19.122(2), c=9.0812(6) Å, Z=2]. All platinum centres have the square-plane D_4h geometry with average dimensions Pt(1)–N 2.042(2) and Pt(2)–N 2.037(10) Å. The octacyanotungstate anion has the square-antiprismatic D_4d configuration with average dimensions W(1)–C 2.164(13), C–N 1.140(12), W(1)–N 3.303(5) Å. The structure exhibits two different mutual orientations of Pt versus W units resulting in Pt(2)–W(1), W(1)^* separations of 4.77(2), 4.55(2)^* and Pt(1)–W(1) of 6.331(8) Å. A centrosymmetric structure reveals groups of two distinct columns: the first is formed by intercalated NO₃⁻ between parallel [Pt(1)(NH₃)₄]²⁺ planes and the second consists of [W(CN)₈]³⁻ interlayered by, parallel to square faces of W-antiprisms, [Pt(2)(NH₃)₄]²⁺. The structure is stabilised through a three-dimensional hydrogen bond network via nitrogen atoms of cyanide ligands, hydrogen atoms of NH₃ ligands, water molecules and oxygen atoms of NO₃⁻ counteranions. The vibrational pattern and the range of ν(CN) frequencies attributable to the electronic environment of W(V) and W(IV) are consistent with the ground state Pt(II)↔W(V) charge transfer.     

Oxidation of organometallic complexes by water: Synthesis of diorgano(hydroxo)platinum(IV) complexes and the structure of a diorgano(aqua)platinum(IV) complex of tris(pyridin-2-yl)methanol, [PtPh2{(py)3COH---N,N′,N″}(OH2)][NO3)2 · H2O

The diorganoplatinum(II) complexes PtR₂{(py)₃COH} (R = Me, Ph; (py)₃COH = tris(pyridin-2-yl)methanol) react with water in organic solvents to form diorgano(hydroxo)platinum(IV) cations [Pt(OH)R₂{(py)₃COH}]⁺, and the cation with R = Ph reacts with dilute nitric acid to form [PtPh₂{(py)₃COH}(OH₂)]²⁺. The cation in [PtPh₂{(py)₃COH}(OH₂)][NO₃]₂ · H₂O has octahedral geometry with a Pt---O bond distance of 2.04(1) Å. The higher trans influence of phenyl than aqua ligands is reflected in the Pt---N bond distances: 2.14(2) and 2.17(1) Å trans to the phenyl groups, and 1.99(2) Å trans to the aqua ligand.     

Synthesis and crystal structure of the heteroleptic lanthanum(III) bis-diphosphinomethanide complex [La{CH(PPh2)2}2(I)(THF)2]

Treatment of CH₂(PPh₂)₂ with n-BuLi/t-BuOK in diethyl ether affords the potassium diphosphinomethanide complex [K{CH(PPh₂)₂}(OEt₂)_0.5] (1) in high yield. Metathesis of two equivalents of 1 with LaI₃(THF)₄ yields the heteroleptic bis-diphosphinomethanide complex [La{CH(PPh₂)₂}₂(I)(THF)₂] (2). X-ray crystallography shows the diphosphinomethanide ligands in 2 adopt different coordination modes in the solid state; one adopts a κ²-PP mode with no La-C contact, and the other adopts an η³-PCP mode, thus giving an eight-coordinate lanthanum centre.     

Chelating diphos ligands with inorganic backbones. Crystal structure of [PtCl2{(PPh2O)2SiPh2}]

The metallo-phosphaalkenes (η⁵-C₅Me₅)(CO)₂FeP=C(R)(SiMe₃) (Ia: R = SiMe₃, Ib: R = Ph) and MeO₂C---CC---CO₂Me undergo a dipolar [3+2]-cycloaddition to afford the metallo-heterocycles [(η⁵-C₅Me₅)(CO)

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=C(R)SiMe₃] (IIIa,b) with exocyclic P=C double bonds.     

Heteroleptic platinum(II) complexes of macrocyclic thioethers and halides: the crystal structures of [Pt(9S3)Cl2], [Pt(9S3)Br2], and [Pt(9S3)I2]

The synthesis, spectroscopic, and crystal structures of three heteroleptic thioether/halide platinum(II) (Pt(II)) complexes of the general formula [Pt(9S3)X₂] (9S3=1,4,7-trithiacyclononane, X=Cl⁻, Br⁻, I⁻) are presented. All three 9S3/dihalo complexes form very similar structures in which the Pt(II) center is surrounded by a cis arrangement of two halides and two sulfur atoms from the 9S3 ligand. The third sulfur from the 9S3 forms a long distance interaction with the Pt center resulting in an elongated square pyramidal structure with a S₂X₂+S₁ coordination geometry. The distances between the Pt(II) center and axial sulfur shorten with larger halide ions (Cl⁻=3.260(3) Å>Br⁻=3.243(2) Å>I⁻=3.207(2) Å). These distances are consistent with the halides functioning as π donor ligands, and their Pt---S axial distances fall intermediate between Pt(II) thioether complexes involving π acceptor and σ donor ligands. The ¹⁹⁵Pt NMR chemical shift values follow a similar trend with an increased shielding of the platinum ion with larger halide ions. The 9S3 ligand is fluxional in all of these complexes, producing a single carbon resonance. Additionally, a related series of homoleptic crown thioether complexes have been studied using ¹⁹⁵Pt NMR, and there is a strong correlation between the chemical shift and complex structure. Homoleptic crown thioethers show the anticipated upfield chemical shifts with increasing number of coordinated sulfurs. Complexes containing four coordinated sulfur donors have chemical shifts that fall in the range of −4000 to −4800 ppm while a value near −5900 ppm is indicative of five coordinated sulfurs. However, for S₄ crown thioether complexes, differences in the stereochemical orientation of lone pair electrons on the sulfur donors can greatly influence the observed ¹⁹⁵Pt NMR chemical shifts, often by several hundred ppm.     

Two new metal derivates of the alumosiloxane [Ph2SiO]8[AlO(OH)]4: [Ph2SiO]8[AlO2(Na)]4 · 5(THF) and [Ph2SiO]8[AlO(OH)]2[AlO2]2[Zn(OH)]2 · 2(OEt2)

When the polycyclic alumosiloxane [Ph₂SiO]₈[AlO(OH)]₄ is allowed to react with either cyclopentadienyl sodium in tetrahydrofuran or with dimethyl zinc in diethyl ether the organic ligands on the metal elements are eliminated as cyclopentadiene or methane and the metals are bonded to oxygen atoms in the alumosiloxane forming [Ph₂SiO]₈[AlO₂(Na)]₄ · 5(THF) or [Ph₂SiO]₈[AlO(OH)]₂[AlO₂]₂[Zn(OH)]₂ · 2(OEt₂), respectively. X-ray structure determinations reveal that in the sodium derivative the original polycycle rests almost unchanged while in the zinc derivative the inner skeleton is rearranged.     

Synthesis and characterisation of the platinum complexes [PtCl(CClPAr)(PPh3)2] and [PtCl(CClPAr′)(PPh3)2] as potential intermediates in the preparation of phosphaalkynes

Oxidative addition reactions of Cl₂CPR (R = 2,4,6-tris(trifluoromethyl)phenyl (Ar) or 2,6-bis(trifluoromethyl)phenyl (Ar′) with Pt(PPh₃)₄ yield the cis and trans (at platinum) complexes [PtCl(ClCPAr)(PPh₃)₂] and [PtCl(ClCPAr′)(PPh₃)₂]. All starting materials and intermediates have been characterised by NMR spectroscopy. The crystal and molecular structures of the trans-platinum complexes have been determined by single-crystal X-ray diffraction at low temperature.     

A novel 2D layer structure constructed from sandwich-type transition metal substituted tungstates and nickel coordination fragments: {[Ni(enMe)2]2[Ni(enMe)2(H2O)]2[As2W18Ni4(enMe)2O68]}·2H3O·2H2O

A novel polyoxometalate {[Ni(enMe)₂]₂[Ni(enMe)₂(H₂O)]₂[As₂W₁₈Ni₄(enMe)₂O₆₈]}·2H₃O·2H₂O (1) (enMe = 1,2-propylenediamine) has been synthesized and characterized, which is the first high-dimensional structure constructed from sandwich-type transition metal substituted tungstates and transition metal coordination groups.     

A novel three-dimensional malonate-bridged complex {[Cu4(4,4′- bpy)8(mal)2(H2O)4](ClO4)2(H2O)4(CH3OH)2}n

A novel malonate-bridged copper (II) compound of formula {[Cu₄(4,4′-bpy)₈(mal)₂(H₂O)₄](ClO₄)₂(H₂O)₄(CH₃OH)₂}_n (4,4′-bpy = 4,4′-bipyridine; mal = malonate dianion) has been prepared and structurally characterized by X-ray crystallography. This compound exhibits a novel three-dimensional network being composed of Cu-4,4′-bipyridine layers which are pillared by malonate bridge ligands. The copper(II) ions has two different coordination environment.     

Combinatorial topology of uranyl molybdate sheets: syntheses and crystal structures of (C6H14N2)3[(UO2)5(MoO4)8](H2O)4 and (C2H10N2)[(UO2)(MoO4)2]

Two new mixed organic-inorganic uranyl molybdates, (C₆H₁₄N₂)₃[(UO₂)₅(MoO₄)₈](H₂O)₄ (1) and (C₂H₁₀N₂)[(UO₂)(MoO₄)₂] (2), have been obtained by hydrothermal methods. The structure of 1 [triclinic, , Z=1, a=11.8557(9), b=11.8702(9), c=12.6746(9) Å, α=96.734(2)°, β=91.107(2)°, γ=110.193(2)°, V=1659.1(2) Å] has been solved by direct methods and refined on the basis of F² for all unique reflections to R1=0.058, which was calculated for the 5642 unique observed reflections (|F_o|?4σ_F). The structure contains topologically novel sheets of uranyl square bipyramids, uranyl pentagonal bipyramids, and MoO₄ tetrahedra, with composition [(UO₂)₅(MoO₄)₈]⁶⁻, that are parallel to (−101). H₂O groups and 1,4-diazabicyclo [2.2.2]-octane (DABCO) molecules are located in the interlayer, where they provide linkage of the sheets. The structure of 2 [triclinic, , Z=2, a=8.4004(4), b=11.2600(5), c=13.1239(6) Å, α=86.112(1)°, β=86.434(1)°, γ=76.544(1)°, V=1203.14(10) Å] has been solved by direct methods and refined on the basis of F² for all unique reflections to R1=0.043, which was calculated for 5491 unique observed reflections (|F_o|?4σ_F). The structure contains topologically novel sheets of uranyl pentagonal bipyramids and MoO₄ tetrahedra, with composition [(UO₂)(MoO₄)₂]²⁻, that are parallel to (110). Ethylenediamine molecules are located in the interlayer, where they provide linkage of the sheets. All known topologies of uranyl molybdate sheets of corner-sharing U and Mo polyhedra can be described by their nodal representations (representations as graphs in which U and Mo polyhedra are given as black and white vertices, respectively). Each topology can be derived from a simple black-and-white graph of six-connected black vertices and three-connected white vertices by deleting some of its segments and white vertices.     

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)2}2V4O12]·5H2O and [Ni(phen)3]2[V4O12]·17.5H2O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen₂)₂V₄O₁₂]·5H₂O (1) and [Ni(phen)₃]₂[V₄O₁₂]·17.5H₂O (2). Crystal data: C₄₈H₅₂Cd₂N₈O₂₂V₄ (1), triclinic. a=10.3366(10), b=11.320(3), c=13.268(3) Å, =103.888(17)°, β=92.256(15)°, γ=107.444(14)°, Z=1; C₇₂H₁₃₁N₁₂Ni₂O_29.5V₄ (2), triclinic. a=12.305(3), b=13.172(6), c=15.133(4), =79.05(3)°, β=76.09(2)°, γ=74.66(3)°, Z=1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59° <θ<26.02° and 2.01°<θ<25.01° using the ω-scan technique, respectively. The structure of 1 consists of a [V₄O₁₂]⁴⁻ cluster covalently attached to two {Cd(phen)₂}²⁺ fragments, in which the [V₄O₁₂]⁴⁻ cluster adopts a chair-like configuration. In the structure of 2, the [V₄O₁₂]⁴⁻ cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the [V₄O₁₂]⁴⁻ unit and crystallization water molecules.     

Synthesis, spectra and crystal structures of two Ru complexes with polypyridyl ligands: cis-[Ru(bpy)2(4,4′-bpy)Cl](PF6)·H2O and cis-[Ru(phen)2(CH3CN)2](PF6)2

Two mononuclear Ru^II complexes of polypyridyl ligands, cis-[Ru(bpy)₂(4,4′-bpy)Cl](PF₆)·H₂O (1) and cis-[Ru(phen)₂(CH₃CN)₂](PF₆)₂ (2) (bpy=2,2′-bipyridyl, 4,4′-bpy=4,4′-bipyridyl, and PHEN=1,10-phenanthroline), have been synthesized and characterized by elemental analyses, IR and UV–vis spectra. The crystal structures of both complexes have been determined by X-ray diffraction, indicating that each Ru^II center is hexa-coordinated (RuN₅Cl for 1 and RuN₆ for 2) and takes a distorted octahedral geometry. The favored feature of both complexes is that they are quite useful complex precursors for further constructing new functional architectures.     

Tuning the sulfur-heterometal interaction in organolead(IV) complexes of [Pt2(μ-S)2(PPh3)4]

Reactions of [Pt₂(μ-S)₂(PPh₃)₄] with Ph₃PbCl, Ph₂PbI₂, Ph₂PbBr₂ and Me₃PbOAc result in the formation of bright yellow to orange solutions containing the cations [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ (R₃ = Ph₃, Ph₂I, Ph₂Br, Me₃) isolated as PF₆⁻ or BPh₄⁻ salts. In the case of the Me₃Pb and Et₃Pb systems, a prolonged reaction time results in formation of the alkylated species [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ (R = Me, Et). X-ray structure determinations on [Pt₂(μ-S)₂(PPh₃)₄PbMe₃]PF₆ and [Pt₂(μ-S)₂(PPh₃)₄PbPh₂I]PF₆ have been carried out, revealing different coordination modes. In the Me₃Pb complex, the (four-coordinate) lead atom binds to a single sulfur atom, while in the Ph₂PbI adduct coordination of both sulfurs results in a five-coordinate lead centre. These differences are related to the electron density on the lead centre, and indicate that the interaction of the heterometal centre with the {Pt₂S₂} metalloligand core can be tuned by variation of the heteroatom substituents. The species [Pt₂(μ-S)₂(PPh₃)₄PbR₃]⁺ display differing fragmentation pathways in their ESI mass spectra, following initial loss of PPh₃ in all cases; for R = Ph, loss of PbPh₂ occurs, yielding [Pt₂(μ-S)₂(PPh₃)₃Ph]⁺, while for R = Me, reductive elimination of ethane gives [Pt₂(μ-S)₂(PPh₃)₃PbMe]⁺, which is followed by loss of CH₄.     

Structural changes accompanying negative thermal expansion in Zr2(MoO4)(PO4)2

Zr₂(MoO₄)(PO₄)₂ is orthorhombic (Sc₂W₃O₁₂ structure) from 9 to at least 400 K, and shows anisotropic volume negative thermal expansion (α_a=−8.35(4)×10⁻⁶ K⁻¹; α_b=3.25(3)×10⁻⁶ K⁻¹; α_c=−8.27(5)×10⁻⁶ K⁻¹ in the range 122-400 K) similar in magnitude to A₂M₃O₁₂ (M—Mo or W) with large A³⁺. The contraction on heating is associated with a pattern of Zr-O-Mo/P bond angle changes that is somewhat similar, but not the same as that for Sc₂W₃O₁₂. On heating, the most pronounced reductions in the separation between the crystallographic positions of neighboring Zr and P are not associated with significant reductions in the corresponding Zr-O-P crystallographic bond angles, in contrast to what was seen for Sc₂W₃O₁₂.     

Solvothermal synthesis and crystal structure of Sb(III) and Sb(V) thioantimonates: [Mn(en)3]2Sb2S5 and [Ni(en)3(Hen)]SbS4

Thioantimonate compounds of [Mn(en)₃]₂Sb₂S₅ (1) and [Ni(en)₃(Hen)]SbS₄ (2) (en=ethylenediamine) were prepared by reaction of transition metal chloride with Sb and S₈ powders under solvothermal conditions. Compound 1 consists of discrete [Sb₂S₅]⁴⁻ anion, which is formed by corner-sharing SbS₃ trigonal pyramids. Compound 2 is composed of discrete tetrahedral [SbS₄]³⁻ anion. The compounds 1 and 2 are charge compensated by [M(en)₃]²⁺ cations, whereas in the crystal of 2 there is another counter ion of [Hen]⁺. The results of the synthesis suggest that the temperature, the concentration and the existing states of the starting materials and so on are important for the structure and composition of the final products. In addition, the oxidation-state of antimony might be related to the molar ratio of the reactants. Excess amount of elemental S is beneficial to the higher oxidation-state of thioantimonate (V). Compound 1 decomposes from 150°C to 350°C, while compound 2 decomposes from 200°C to 350°C remaining Sb₂S₃ and NiSbS as residues.