A 2-iridathiophene from reaction between IrCl(CS)(PPh3)2 and Hg(CHCHPh)2

The thiocarbonyl analogue of Vaska’s compound is produced in high yield by first treating IrCl(CO)(PPh₃)₂ with CS₂ and methyl triflate to give [Ir(κ²-C[S]SMe)Cl(CO)(PPh₃)₂]CF₃SO₃ (1), secondly, reacting 1 with NaBH₄ to give IrHCl(C[S]SMe)(CO)(PPh₃)₂ (2), and finally heating 2 to induce elimination of both MeSH and CO to produce IrCl(CS)(PPh₃)₂ (3). When IrCl(CS)(PPh₃)₂ is treated with Hg(CHCHPh)₂ the novel 2-iridathiophene, Ir[SC₃H(Ph-3)(CHCHPh-5)]HCl(PPh₃)₂ (4) is produced. The X-ray crystal structure of the iodo-derivative of 4, Ir[SC₃H(Ph-3)(CHCHPh-5)]HI(PPh₃)₂ (5) confirms the unusual 2-metallathiophene structure. Treatment of IrCl(CS)(PPh₃)₂ with Hg(CHCPh₂)₂ produces both a coordinatively unsaturated 1-iridaindene, Ir[C₈H₅(Ph-3)]Cl(PPh₃)₂ (6) and a chelated dithiocarboxylate complex, Ir(κ²-S₂CCHCPh₂)Cl(CHCPh₂)(PPh₃)₂ (7). X-ray crystal structure determinations for 6 and 7 are reported.     

A novel arene bonding mode in the mixed-metal cluster Os4Ru(μ-H) 3(CO) 12(μ3-η-C6H5) P(OMe)3

The ionic coupling of [Os₄H₂(CO)₁₂]²⁻ with [Ru(η⁶-C₆H₆)(MeCN)₃]²⁺ affords the neutral mixed metal cluster Os₄Ru(μH)₂(CO)₁₂(η⁶-C₆H₆) 1. The reaction of 1 with trimethylphosphite leads to the initial formation of the addition product Os₄Ru(μH)₂(CO)₁₂(η⁶-C₆H₆)P(OMe)₃ 2, but this complex rearranges in solution to give Os₄Ru(μ-H)₃(CO)₁₂(μ₃-η⁶-C₆H₅)P(OMe)₃ 3. An X-ray structure of 3 shows that the metal core of the cluster is a ruthenium-spiked Os₄ tetrahedron, with one hydrogen atom from the arene having transferred to the Os₄ core, and one arene carbon bridging an Os-Os edge, while the ring as a whole remains η⁶-bound to the Ru atom.     

Synthesis and X-ray crystal structures of [Ru4H4(CO) 11(PPh3)] and [Ru4−x IrxH2−x(CO) 12(PPh3) ] (x = 0 or 1)

Three tetranuclear clusters [Ru₄H₄(CO)₁₁(PPh₃)] (1), [Ru₄H₂(CO)₁₂(PPh₃)] (2) and [Ru₃IrH(CO)₁₂(PPh₃)] (3) were formed in the reaction of [Ir(CO)Cl(PPh₃)₂] and Na[Ru₃H(CO)₁₁] in tetrahydrofuran. Complexes 1–3 were characterized by IR and ¹H and ³¹P NMR, and the structure of the clusters was confirmed by single crystal X-ray analysis. In 2 and 3 one of the carbonyls bridges between two ruthenium atoms; otherwise the compounds contain only terminal carbonyls.     

Formation and structural characterization of novel polynuclear palladium selenolato complexes [Pd3Se(SePh)3(PPh3)3]Cl and [Pd6Cl2Se4(SePh)2(PPh3)6]

In addition to well-known dinuclear phenylselenolato palladium complexes, the reaction of [PdCl₂(PPh₃)₂] and NaSePh affords small amounts of novel trinuclear and hexanuclear complexes [Pd₃Se(SePh)₃(PPh₃)₃]Cl (1) and [Pd₆Cl₂Se₄(SePh)₂(PPh₃)₆] (2). Complex 1 is triclinic, P1?, a=13.6310(2), b=16.2596(2), c=16.9899(3) Å, α=83.1738(5), β=78.9882(5), γ=78.7635(5)°. Complex 2 is monoclinic, C2/c, a=25.7165(9), b=17.6426(8), c=27.9151(14) Å, β=110.513(2)°. There are no structural forerunners for 1, but the hexanuclear complex 2 is isostructural with [Pd₆Cl₂Te₄(TeR)₂(PPh₃)₆] (R=Ph, C₄H₃S) that have been observed as one of the products in the oxidative addition of R₂Te₂ to [Pd(PPh₃)₄]. Mononuclear palladium complexes may play a significant role as building blocks in the formation of the polynuclear complexes.     

Synthesis,characterization and antimicrobial studies of mixed ligand silver(I) complexes of thioureas and triphenylphosphine; crystal structure of {[Ag(PPh3)(thiourea)(NO3)]2·[Ag(PPh3)(thiourea)]2(NO3)2}

Mixed ligand silver(I) complexes of triphenylphosphine and thioureas (thiourea (Tu), N-methylthiourea (Metu), N,N′-dimethylthiourea (Dmtu) and N,N′-diethylthiourea (Detu)) with the general formulae, [(Ph₃P)₂Ag(thione)]NO₃ and [(Ph₃P)Ag(thione)₂]NO₃, have been prepared and characterized by elemental analysis, IR and NMR (¹H, ¹³C and ³¹P) spectroscopic methods. The crystal structure of one of them has been determined by X-ray crystallography. The spectral data of the complexes are consistent with sulfur coordination of the thiones to silver(I). The single crystal X-ray structure of complex 1, {[Ag(PPh₃)(thiourea)(NO₃)]₂·[Ag(PPh₃)(thiourea)]₂(NO₃)₂}, shows that the complex consists of two independent centrosymmetric binuclear units, each having the silver atoms coordinated to one PPh₃ and two bridging thiourea molecules. In one of the independent units the silver atom is additionally bound to a nitrate ion, leading to a tetrahedral geometry, while in the other unit the silver atom adopts a trigonal planar environment. Antimicrobial activities of the complexes were evaluated by their minimum inhibitory concentration and the results showed that the complexes show a wide range of activity against two gram-negative bacteria (Escherichiacoli, Pseudomonasaeruginosa) and molds (Aspergillusniger, Penicilliumcitrinum), while the activities were poor against yeasts (Candidaalbicans, Saccharomycescerevisiae). However, the title complex did not show activity against any tested microorganism.     

Multiple ligand transfer reaction between [CpRu(L)(AN)2][PF6] (L=AN, CO, P(OMe)3; AN=acetonitrile) and CpFe(CO)L′X (L′=CO, PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X=Cl, Br, I)

Treatment of ruthenium complexes [CpRu(AN)₃][PF₆] (1a) (AN=acetonitrile) with iron complexes CpFe(CO)₂X (2a–2c) (X=Cl, Br, I) and CpFe(CO)L′X (6a–6g) (L′=PMe₃, PMe₂Ph, PMePh₂, PPh₃, P(OPh)₃; X=Cl, Br, I) in refluxing CH₂Cl₂ for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)₂X (3a–3c) (X=Cl, Br, I) and CpRu(CO)L′X (7a–7g) (L′=PMe₃, PMe₂Ph, PMePh₂, PPh₃, P(OPh)₃; X=Br, I), respectively. Similar reaction of [CpRu(L)(AN)₂][PF₆] (1b: L=CO, 1c: P(OMe)₃) causes double ligand transfer to yield complexes 3a–3c and 7a–7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]₂ was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH₂Cl₂ at room temperature to give 3a, and transforms into 7a by the reaction with PMe₃.     

Reaction of [CpRu(CH3CN)3]PF6 with bidentate ligands: structural characterization of [{CpRu(CH3CN)2}2(μ-η-dppe)](PF6)2 [dppe=1,2-bis(diphenylphosphino)ethane]

The reaction of [CpRu(CH₃CN)₃]PF₆ with the bidentate ligands L-L=1,2-bis(diphenylphosphino)ethane, dppe, and (1-diphenylarsino-2-diphenylphosphino)ethane, dpadppe, affords mononuclear or dinuclear complexes of formula [CpRu(η²-L-L)(CH₃CN)]PF₆, [{CpRu(CH₃CN)₂}₂(μ-η^1:1-L-L)](PF₆)₂ and [{CpRu(CH₃CN)}₂(μ-η^1:1-L-L)₂](PF₆)₂ (L-L=dppe, dpadppe). All of the compounds are characterized by microanalysis and NMR [¹H and ³¹P{¹H}] spectroscopy. The crystal structure of [{CpRu(CH₃CN)₂}₂(μ-η^1:1-dppe)](PF₆)₂ has been determined by X-ray diffraction analysis. The complex exhibits a dppe ligand bridging two CpRu(CH₃CN)₂ fragments.     

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.     

The reactions of 2-benzoylpyridine with [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2

The reactions of [RuHCl(CO)(PPh₃)₃] and [(C₆H₆)RuCl₂]₂ with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh₃)₂(C₅H₄NCOO)] and [RuCl₂(C₁₂H₉NO)₂] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.     

The reactions between [RuHCl(CO)(PPh3)3] and quinoline carboxylic acids

The reactions of [RuHCl(CO)(PPh₃)₃] with 8-hydroxy-2-methyl-quinoline-7-carboxylic acid and quinoline-2-carboxylic acid have been examined, and two novel ruthenium(II) complexes – [(PPh₃)₂RuH(CO)(C₁₀H₈NO₃)] and [(PPh₃)₂RuCl(CO)(C₉H₆O₂)] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.     

The tris(triphenylphosphine)osmium zerovalent complexes Os(CO)2(PPh3)3, .Os(CO)(CNR)(PPh3)3, Os(CO)(CS)(PPh3)3, Os(CS)(cNR)(PPh3)3 and derived compounds

Detailed procedures for the syntheses of Os(CO)₂(PPh₃)₃, Os(CO)(CNR)-(PPh₃)₃ (R = p-tolyl), Os(CO)(CS)(PPh₃)₃ and Os(CS)(CNR)(PPh₃)₃, together with the derived complexes Os(CO)₂(CS)(PPh₃)₂, Os(CO)(CS)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CNR)(PPh₃)₂, Os(η²-C₂H₄)(CO)(CS)(PPh₃)₂, Os(η²CS₂)(CO)₂-(PPh₃)₂, Os(η²CS₂)(CO)(CS)(PPh₃)₂, Os(η²-CS₂)(CO)(CNR)(PPh₃)₂, Os(η²PhC₂Ph)(CO)₂(PPh₃)₂ and OsH(C2Ph)(CO)₂(PPh₃)₂ are described.     

High-nuclearity ruthenium carbonyl cluster chemistry. 8: Phosphine activation, CO insertion, and deruthenation at a phosphido cluster - X-ray structures of [ppn][Ru8(μ8-P)(μ-CO)2(CO)20] and [ppn][Ru7(μ7-P)(μ-η-OCPh)(μ-PPh2)(μ-CO)(CO)17]

Reaction of the square antiprismatic cluster [ppn][Ru₈(μ₈-P)(μ-CO)₂(CO)₂₀] [ppn = bis(triphenylphosphoranylidene)ammonium] with triphenylphosphine proceeds by loss of one cluster core vertex, phosphine P-C cleavage, and CO insertion into the putative Ru-phenyl bond to afford [ppn][Ru₇(μ₇-P)(μ-η²-OCPh)(μ-PPh₂)(μ-CO)(CO)₁₇] in low yield, the first heptaruthenium μ₇-phosphido-ligated cluster.     

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.     

Thiocarbonyl complexes of ruthenium(II). Synthesis of RuCl2(CS)(H2O)(PPh3)2 and RuHCl(CS)(PPh3)3

A high-yield synthesis of trans-RuCl₂(CS)(H₂O)(PPh₃)₂ from RuCl₂(PPh₃)₃ and CS₂ is described. The coordinated water molecule is labile, and introduction of CNR (R  p-toyl or p-chlorophenyl) leads to yellow trans-RuCl₂(CS)(CNR)(PPh₃)₂, which isomerises thermally to colourless cis-RuCl₂(CS)(CNR)(PPh₃)₂. Reaction of AgClO₄ with cis-RuCl₂(CS)(CNR)(PPh₃)₂ gives [RuCl(CS)(CNR)(H₂O)(PPh₃)₂]⁺, from which [RuCl(CS)(CO)(CNR)(PPh₃)₂]⁺ and [RuCl(CS)(CNR)₂(PPh₃)₂]⁺ are derived. Reaction of trans-RuCl₂(CS)(H₂O)(PPh₃)₂ with sodium formate gives Ru(η²-O₂CH)Cl(CS)(PPh₃)₂, which undergoes decarboxylation in the presence of (PPh₃) to give RuHCl(CS)(PPh₃)₃. Ru(η²-O₂CH)H(CS)(PPh₃)₂ and Ru(η²-O₂CMe)-H(CS)(PPh₃)₂ are also described.     

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.     

Syntheses and crystal structures of linear coordinated complexes of Ag with the ligands C(PPh3)2 and (HC{PPh3}2)

The cationic complexes [({Ph₃P}₂C)Ag(C{PPh₃}₂)]X (2⁺, X = Cl, BF₄) with a linear arrangement of the ligands were obtained from the reaction of C(PPh₃)₂ (1) with the appropriate AgX in THF. The ³¹P NMR spectrum of the cation 2⁺ exhibits a doublet with J(Ag,P) = 15.3 Hz. The cation was also formed when the adduct O₂C ← 1 was allowed to react with AgX in CH₂Cl₂ in the first step as shown by ³¹P NMR; however, deprotonation of the solvent finally produced the cation (HC{PPh₃}₂)⁺, (H1)⁺ quantitatively. In the absence of coordinating anions, the tricationic complex [({Ph₃P}₂CH)Ag(CH{PPh₃}₂)](BF₄)₃ (3), containing the cation (H1)⁺ as ligand, could be isolated by reacting AgBF₄ with the salt (H1)(BF₄). All compounds were characterized by IR and ³¹P NMR spectroscopy; the structures of the compounds [2]Cl·1.25THF, 3·5CH₂Cl₂, 3·4C₂H₄Cl₂, and (H1)(BF₄) could be established by X-ray analyses.     

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…     

Mixed-metal cluster chemistry VI: Phosphine substitution at CpMoIr3(μ-CO)3(CO)8; X-ray crystal structure of CpMoIr3(μ-CO)3(CO)7(PPh3)

Reactions of CpMoIr₃(μ-CO)₃(CO)₈ (1) with stoichiometric amounts of phosphines afford the substitution products CpMoIr₃(μ-CO)₃(CO)_8−x (L)_x (L = PPh₃, x = 1 (2), 2 (3); L = PMe₃, x = 1 (4), 2 (5), 3 (6)) in fair to good yields (23–54%); the yields of both 3 and 6 are increased on reacting 1 with excess phosphine. Products 2–5 are fluxional in solution, with the interconverting isomers resolvable at low temperatures. A structural study of one isomer of 2 reveals that the three edges of an MoIr₂ face of the tetrahedral core are spanned by bridging carbonyls, and that the iridium-bound triphenyiphosphine ligates radially and the molybdenum-bound cyclopentadienyl coordinates axially with respect to this Molr₂ face. Information from this crystal structure, ³¹P NMR data (both solution and solid-state), and results with analogous tungsten—triiridium and tetrairidium clusters have been employed to suggest coordination geometries for the isomeric derivatives.     

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.     

New heterodimetallic cyclopentadienyl carbonyl complexes: crystal structure of (C5Me4Et)(μ-CO)3Ru(C5Me5)

A series of heterodimetallic complexes of general formula (C₅R₅)M(μ-CO)₃RuC₅Me₅ (M = Cr, Mo, W; R = Me, Et) has been prepared in good yields by the reaction of [C₅R₅M(CO)₃]⁻ with [C₅Me₅Ru(CH₃CN)₃]⁺. (C₅Me₄Et)W(μ-CO)₃Ru(C₅Me₅) was characterized by a crystal structure determination. The W---Ru bond length of 2.41 Å is consistent with the formulation of a metal-metal triple bond, while the unsymmetrical bonding mode of the three bridging carbonyl groups reflects the inherent non-equivalence of the two different C₅R₅M-units. Using [CpRu(CH₃CN)₃]⁺ or [CpRu(CO)₂(CH₃CN)]⁺ as the cationic precursor leads to the formation of dimetallic species (C₅R₅)M(CO)₅RuC₅H₅ with both bridging and terminal carbonyl groups.