Reaktionen von Nitrosylkomplexen: VIII. Ein alternativer Weg zu Cp3Co3(μ3-NO)2 sowie Synthese des isoelektronischen Clusters Cp3Co2Fe(μ3-NH)(μ3-NO)

Treatment of CpCo(C₂H₄)₂ with NO in hexane yields Cp₃Co₃(μ₃-NO)₂ together with the dinitrosoethane complex CpCo(NO)₂C₂H₄; the mixture of these known compounds can easily be separated. The reaction of [CpFeNO]₂ with excess CpCo(C₂H₄)₂ in THF gives Cp₃Co₂Fe(μ₃-NH)(μ₃-NO) as the main product, which is an isoelectronic congener of Cp₃Co₃(μ₃-NO)₂. Another isoelectronic species of possible composition Cp₃CoFe₂(μ₃-NH)₂ is found as a by-product.     

Reaktionen von [CpRuOMe]2: XI. Austausch mit Thiolen und Molekülstruktur von [C5Me4EtRuSEt]2

Complexes [CpRuSR]₂ and [Cp RuSR]₂, where Cp = η⁵-C₅Me₅, Cp = η⁵-C₅Me₄Et, R Et, ^tBu, (^tBuO)₃Si, are synthesized by exchange of the metboxo groups in [CpRuOMe]₂ with the respective thiols. An X-ray molecular structure determination of [Cp RuSEt]₂ confirms the dimeric structure with co-ordinatively unsaturated 16 VE Ru. The molecular geometry of the thiol-bridged dimer is compared to that of the oxo analogue.     

Synthese von substituierten 2-(Ethoxycarbonyl-formyl-methylen)-2H-benzopyranen und ihre Überführung in Polymethinderivate

Summary 3-Chloro-2-ethoxycarbonyl crotonic aldehydeC reacts with several 2-hydroxybenzene carbaldehydes and 2-hydroxy-naphthalene-1-carbaldehyde, respectively, to give 2-(ethoxycarbonyl-formyl-methylene)-2H-benzopyrans1a–h under mild conditions. With exception of1c and1d these compounds are mixtures ofE–Z isomers.1a–h easily undergo reactions, e.g. with aniline and derivatives to give2a–e, with various CH-acidic compounds to give3a–h and with 2-alkyl-4,6-diphenyl pyrylium salts to give4a–e. In the presence of alcoholic hydrochloric acid, compounds1 are converted into symmetrical 2,2-benzopyrylotrimethine salts5a–e which exhibit longwave absorptions from 640–705 nm. These polymethine dyes with ester groups in the methine chain exhibit a remarkable thermal stability.

     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2′-bpy)_3]_2[Co(2,2′-bpy)_2Cl][Co(2,2′-bpy)_2]H_2- [SbW_(18)O_(60)]·4H_2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9, formulated [Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2[SbW18O60]·4H2O (2,2′-bpy= 2,2′-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2′-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9 en- capsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoII and low-spin CoII ions coexist in the title compound. Magnetic properties in- dicate that the compound is antiferromagnetic.     

Novel polyselenidoarsenate and selenidoarsenate: solvothermal synthesis and characterization of [Co(phen)3][As2Se2(μ-Se3)(μ-Se5)] and [Co(phen)3]2[As8Se14

Novel cobalt polyselenidoarsenate [Co(phen)(3)][As(2)Se(2)(μ-Se(3))(μ-Se(5))] (1; phen = 1,10-phenanthroline) was methanolothermally synthesized by the reaction of CoCl(2), As(2)O(3), and Se templated by phen in a CH(3)OH solvent at 130 °C. The same reaction in a H(2)O solvent yielded cobalt selenidoarsenate [Co(phen)(3)](2)[As(8)Se(14)] (2). In 1, the AsSe(+) units are alternately joined by the μ-Se(3)(2-) and μ-Se(5)(2-) bridging ligands to form a novel helical polyselenidoarsenate chain [As(2)Se(2)(μ-Se(3))(μ-Se(5))(2-)](∞). In 2, eight pyramidal AsSe(3) units are connected via corner sharing into the new member of the selenidoarsenate aggregate [As(8)Se(14)](4-) with a condensation grade of 0.571, which represents the first discrete selenidoarsenate(III) with a condensation grade of above 0.50. The octahedral complex [Co(phen)(3)](2+) is formed in situ to act as a countercation in compounds 1 and 2. 1 and 2 exhibit steep absorption band gaps at 2.09 and 2.16 eV, respectively.     

Übergangsmetall-heteroallen-komplexe: XIII. Reaktionen der cobalt-thioketen-komplexe [Co(R2CCS)(C5H5)] mit elektrophilen

Reaction of the η²(C,S)-coordinated thioketene cobalt complex [Co(C₁₁H₁₈S)-(PMe₃(C₅H₅)] (2a) with the electrophils [Mn(CO)₂(THF)(C₅H₅] and [Cr(CO)₅(THF)] gives the dinuclear thioketene complexes (4) with two different metal atoms in the molecule. The structure of the cobalt manganese compound was determined by X-ray diffraction. Protonation of the mononuclear thioketene complexes 2 give novel cationic η²-bonded thioacyl compounds [Co(η²-RCS)-(PMe₃(C₅H₅)]⁺ (9), as confirmed by X-ray analysis.     

Synthesis and Characterization of Nitrato-Triamine-Metal(II) Complexes. Conglomerate Crystallization Part 55. Crystal Structure of [Ni(dien)(O2NO)(ONO2)] (I), {[Cu(dien)-(μ-ONO2)]NO3}∞ (II), [Zn(dien)(O2NO)(ONO2)] (III), [Ni(Medpt)(O2NO)(ONO2)] (IV) and [Cu(Medpt)(ONO2)2] (V)

In absolute ethanol and in the presence of triethylorthoformate, reactions of metal(II) nitrates with linear tridentate amines afforded metal complexes of the formula M(NNN)(NO₃)₂, where M = Ni²⁺, Cu²⁺ and Zn²⁺, and NNN = dien and Medpt. The compounds fall into three categories in accordance with their stereochemistry and mode of binding of the nitrato ligands. Compounds I, [Ni(dien)(O₂NO)(ONO₂)] and III, [Zn(dien)(O₂NO)(ONO₂)] are isomorphous and isostructural. They crystallize in the monoclinic space group P2₁/n with nearly identical cell constants. The stereochemistry of these two compounds is such that the terdentate dien ligand forms a fac MN₃ moiety with the two oxygens of the bidentate nitrato ligand trans to the terminal NH₂. These ligands form the base of the octahedral arrangement in which the sixth position, trans to the secondary nitrogen of the dien, is an oxygen of the monodentate nitrato ligand. Compound IV, [Ni(Medpt)(O₂NO)(ONO₂)] falls into the same category as I and III despite the fact that the two rings in the Ni-Medpt moiety are six-membered rings, unlike those in compounds I and III which are five-membered rings. Nevertheless, the nickel-amine arrangement is fac. The bidentate nitrato-oxygens are trans to the terminal NH₂ of the amine ligand, and the oxygen of the monodentate nitrato ligand is trans to the tertiary amine-nitrogen. Such stereochemistry is prevalent for nickel and zinc compounds. Interestingly, compound IV crystallizes as a conglomerate (space group P2₁2₁2₁). Compound II, {[Cu(dien)(μ-ONO₂)]NO₃}_∞ belongs to the second category and has a polymeric structure. The repeating fragment in the polymeric chain is a Cu(dien)-O fragment with the monodentate nitrato ligand occupying an equatorial position of the base. A second oxygen of the equatorial nitrate becomes an axial ligand for an adjacent Cu-N₃O fragment. In this way the substance propagates into an infinite chain. The repeating unit has an effective square pyramidal, five-coordinate, configuration. Finally, the compound crystallizes as a racemate. The second nitrate necessary for charge compensation of this copper(II) compound is ionic and its function is to hold the infinite chains of the lattice. The third category represented by compound V, [Cu(Medpt)(ONO₂)₂] contains two molecules in the asymmetric unit of the racemic lattice (monoclinic, space group P2₁/a). The structure of Cu-Medpt is unlike that of IV in that both species present in the asymmetric unit have the amine ligand in a mer configuration which together with a monodentate oxygen of a nitrato ligand form a base plane of a square pyramid. The fifth ligand of both Cu²⁺ ions is a second monodentate nitrato ligand. The stereochemical differences between the two Cu²⁺ ions are insignificant for the Cu-Medpt fragment, which share the same conformation and configuration. The major difference between the two species is the torsional angles defined by the Cu-O-N-O angles. The difference arises from variation in the hydrogens of the primary amine moieties selected by nitrato-oxygens to form intramolecular hydrogen bonds. Finally, there is a little variation in the equatorial Cu-ONO₂ stereochemistry because of steric hindrance, imposed by the Medpt, preventing large torsional angles by these nitrato ligands. This is evident by comparing the two copper species shown in Finally, nitrate-to-Br ligand exchange was found to take place when KBr pellets are prepared for IR spectral measurements.     

Metallkomplexe mit verbrückenden dimethylphosphido-liganden: IV. Additions- und insertionsreaktionen von [C5H5Co(μ-PMe2)]2 mit schwefel,selen un tellur

The complex [C₅H₅Co(μ-PMe₂)]₂ reacts with sulphur, selenium and tellurium at room temperature to give the compounds [(C₅H₅Co)₂(μ-PMe₂)₂(μ-E)] (IV: E = S; VI: E = Se; VIII: E = Te) and [(C₅H₅Co)₂(μ-PMe₂)(μ-EPMe₂)] (V: E = S; VII: E = Se). By using grey selenium, compound VI is predominantly obtained, whereas with the red form of Se, compound VII is the main product. The nucleophilic behaviour of the bridging-chalcogen atoms in the dinuclear complexes IV, VI and VIII is characterised by their reaction with CF₃CO₂H/NH₄PF₆, CH₃I, CH₂ClI and C₅H₅Mn(CO)₂THF from which the compounds [(C₅H₅Co)₂(μ-PMe₂)₂(μ-EH)]PF₆, [(C₅H₅Co)₂(μ-PMe₂)₂(μ-ECH₃)]I, [(C₅H₅Co)₂(μ-PMe₂)₂(μ-SeCH₂Cl)]PF₆ and [(C₅H₅Co)₂(μ-PMe₂)₂(μ-EMn(CO)₂C₅H₅)] are obtained. The proposed structure of these complexes is discussed on the basis of their ¹H and ³¹P NMR spectra.     

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.     

新型有机-无机杂化的类Dawson型多金属钨酸盐[Co(2,2′-bpy)_3]_2[Co(2,2′-bpy)_2Cl][Co(2,2′-bpy)_2]H_2-[SbW_(18)O_(60)]·4H_2O的合成、晶体结构及性质

以Sb2O3、Na2WO4、CoCl2及2,2′-联吡啶为原料,采用水热合成方法,制得了新颖的有机-无机杂化的类Dawson型多金属氧酸盐:[Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2-[SbW18O60]·4H2O(2,2′-bpy=2,2′-bipyridine),并通过元素分析,IR,XPS,EPR,TG,变温磁化率和X-射线单晶衍射等分析手段对化合物进行表征.X-射线单晶衍射测定表明,该化合物属于正交晶系,Pba2空间群,晶胞参数:a=2.1208(2)nm,b=2.4506(2)nm,c=1.2931(1)nm,Z=2,R1=0.0416,wR2=0.0771.晶体解析表明,Sb2O3与Na2WO4在水热条件下组装成少见的类Dawson型多金属氧酸盐阴离子[SbW18O60]9-,该阴离子的{W18}簇结构骨架中包含一个三角锥形{SbO3}基团.EPR谱分析表明,高自旋态和低自旋态Co2 共存于标题化合物中.磁性质研究表明标题化合物显示抗磁性.     

OBERFLÄCHEN-REAKTIONEN 151,2 Heterogen Dechlorierungen von Phosphorchloriden (X)PCI3 und R[sbnd]PCI2 an [Ag], [Mg], [Cux/TiO2] und [MgCI2[sbnd]MgO/SiO2] sowie spektroskopische Evidenz für das Entstehen von Diphospha-dicyan P[tbnd]C[sbnd]C[tbnd]P aus CI2P[sbnd][tbnd][sbnd]PCI2

Abstract

Stimulated by the successful generation of unsaturated molecules with low-coordinated phosphorus centers by heterogeneous surface dechlorination, CI₂,P[sbnd]C[tbnd]C[sbnd]PCI², is synthesized and characterized by PE and mass spectra. In addition, [Mg] curls, [Ag] wool and catalysts [Cu_x/TiO₂] or [MgCI₂,[sbnd]MgO/SiO₂] are tested as potential dechlorinating agents for phosphorus halides like OPCI₃, SPCI₃, H₃C[sbnd]PCI₂, H₅C₂-PCI₂, (H₃C)₃C[sbnd]PCI₂, or H₅C₆-PCI₂, in a gasflow reactor under reduced pressure and yield, inter aha, the following representative results: due to the thermodynamically favored formation of [MgCl₂], [MgO] or [MgS] at the Mg surface, P₄ is the only gaseous product identified from reactions of OPCI₃, and SPCI₃, with [Mg] metal at higher temperatures. On the contrary, passing H₃C-PCI₂, at 600K over [Mg] yields a reaction mixture containing P(CH₃)₃,(H₃C)₂P[sbnd]P(CH₃)₂, (H₃C[sbnd]P), and CH₄, which suggests an intermediate formation of surface phosphinidenes [H₃C[sbnd]P →Mg]. Analogously, the pentamer (H₃C[sbnd]H₂C[sbnd]P)₅ can be isolated from ethyldichlorophosphane. Reaction of the evaporated diphospha-cyanogen precursor CI₂P[sbnd]C[tbnd]C[sbnd]PCI₂ with the catalyst [10% MgCI₂,/MgO/SiO₂], produces predominantly PCI₃, and P₄, but PE and mass spectra provide evidence that also minor amounts of the hitherto unknown molecule P[tbnd]C[sbnd]C[tbnd]P are formed.     

Coordination Networks Self-assembled by Transition Metal Salts With 4,4′-oxydianiline (4,4′-oda). Syntheses and Structures of ∞ 1 [Ni(NCS) 2 (4,4′-oda) 2 ], ∞ 2 [Co(NCS) 2 (4,4′-oda) 2 ] and ∞ 2 [M(N 3 )(4,4′-oda) 2 ]NO 3 (M=Cd II or Co II )

Four infinite complexes X 1 [Ni(NCS) 2 (4,4'-oda) 2 ], X 2 [Co(NCS) 2 (4,4'-oda) 2 ] and X 2 [M(N 3 )(4,4'-oda) 2 ]NO 3 [M=Cd II ( 3 ) or Co II ( 4 )] were obtained by reactions 4,4'-oxydianiline (4,4'-oda) with Ni(SCN) 2 , Co(SCN) 2 , Cd(N 3 ) 2 and Co(N 3 ) 2 , respectively which have been structurally established by single-crystal X-ray diffraction. Complex 1 contains one-dimensional double-stranded chains comprising 24-membered Ni 2 (4,4'-oda) 2 macrocycles, each formed by two 4,4'-oda ligands and two octahedral Ni II centers. Complex 2 exhibits two-dimensional non-interpenetrating networks consisting of large 48-membered macrocycles each formed by four 4,4'-oda ligands and four octahedral Co II centers. The crystal structures of 3 and 4 are isomorphous and both contain one-dimensional double-stranded chains comprising 24-membered M 2 (4,4'-oda) 2 macrocycles, which are interlinked by w -1,3-azide groups to generate cationic two-dimensional sheets. These sheets are further connected by hydrogen bonds between the amine groups and nitrate ions to furnish three-dimensional networks. Crystal data: complex 1 crystallizes in the monoclinic space group P 2 1 / c with a =11.990(4) Å, b =9.413(4) Å, c =12.827(4) Å, g =116.32(2), V =1297.6(8) Å 3 and Z =2; complex 2 crystallizes in the orthorhombic space group Pbca with a =9.583(2) Å, b =12.738(3) Å, c =21.039(4) Å, V =2568.2(9) Å 3 and Z =4; complex 3 crystallizes in the monoclinic space group C 2/ c with a =23.036(5) Å, b =5.920(1) Å, c =17.800(4) Å, g = 92.67(3), V =2424.8(9) Å 3 and Z =4; complex 4 crystallizes in the monoclinic space group C 2/ c with a = 22.861(5) Å, b =5.812(1) Å, c =17.720(4) Å, g =93.00(3), V =2351.2(8) Å 3 and Z =4.     

A new organic-inorganic hybrid material constructed from Keggin polyanion and transition metal complexes: [Co(2,2′-bipy)3]1.5[SiWVWVI 11O40Co(2,2′-bipy)2(H2O)] · 0.5H2O

A new organic-inorganic hybrid compound constructed from Keggin-type polyanion clusters and transition metal complexes, [Co(2,2′-bipy)₃]_1.5[SiW^VW^VI ₁₁O₄₀Co(2,2′-bipy)₂(H₂O)] ·?0.5H₂O (1), has been hydrothermally prepared and characterized by elemental analysis, IR, UV–Vis, TG-DTA and single crystal X-ray diffraction. Compound 1 crystallized in the monoclinic system, space group C2/c, a =?46.995(15), b =?14.487(5), c =?26.205(9)Å, β =?90.000(0)°, V =?17841(10)ų, Z =?4. Compound 1 contains a [SiW^VW^VI ₁₁O₄₀Co(2,2′-bipy)₂(H₂O)]^3? polyoxoanion in which [Co(2,2′-bipy)₂(H₂O)]²⁺ is covalently bonded to the α-Keggin-type heteropolyanion [SiW^VW^VI ₁₁O₄₀]^5? via a terminal oxygen.     

Synthesis and crystal structure of platinum(II) acetamidates [Pt(2,2′-bipy)(NHCOCH3)2] and [enPt(μ-NHCOCH3)(μ-OH)Pten](NO3)2

The diamines PtbipyCl₂, and PtenCl₂ and their aqua and hydroxy derivatives react with acetonitrile to give the Pt(II) acetamidates [Pt(2,2′-bipy)(NHCOCH₃)₂] · 4.125 H₂O (I) and [enPt(μ-NHCOCH₃(μ-OH)Pten](NO₃)₂ · H₂O (II), which are characterized by X-ray diffraction. The crystals of I are triclinic, a = 7.137(10) Å, b = 12.655(3) Å, c = 21.914(6) Å, α = 81.82(2)°, β = 82.12(2)°, γ = 77.72(2)°, V = 1908.6(7) ų, space group P $\overline 1 $ , Z = 4, R = 0.033 for 3700 reflections. Complex I is a mononuclear acetamidate with terminal (NHCOCH₃)^? ligands. The crystals of II are monoclinic, a = 11.413(2) Å, b = 10.981(2) Å, c = 14.385(3) Å, β = 105.90(3)°, V = 1733.8(6) ų, space group P2₁/n, R = 0.028 for 2797 reflections. Complex II is a dimer with bridging (NHCOCH₃)^? and (OH)^? groups. The Pt-Pt distance is 3.1667(7) Å.     

Synthese und kristallstrukturuntersuchung von bis[dicarbonyl(μ-trifluormethylisocyanid)-(η-pentamethylcyclopentadienyl)molybdän)], [Mo(CO)2(μ-CNCF3)(η-Cp)]2 und dessen isomerisierung zu Cp(CO)2Mo(μ-F3CNCCNCF3)Mo(CO)2Cp

Trifluoromethyl isocyanide adds to the metal—metal triple bond of bis[dicarbonyl(η-pentamethylcyclopentadienyl)molybdenum] forming Mo₂Cp₂(CO)₄(η²-μ-CNCF₃) as the first isolated product. Further addition of trifluoromethyl isocyanide at 0°C leads to the formation of [Mo(CO)₂(μ-CNCF₃)(η-Cp)]₂, which according to crystal structure analysis contains two bridging CF₃NC ligands. During the isomerization of this compound in dichloromethane solution at room temperature or in the solid state above 110°C molybdenum—molybdenum bond cleavage and carbon—carbon bond formation occurs, leading to Cp(CO)₂Mo(μ-F₃CNCCNCF₃)Mo(CO)₂Cp, which contains 1,1,1,6,6,6-hexafluoro-2,5-diaza-2,3,4-hexatriene as bridging ligand.     

Reactions of dipropargyl manolate,terephthalate with Co2(CO)8, Mo2Cp2(CO)4 and RuCo2(CO)11 give the di or tetranuclear clusters. The crystal structure of [CH2(CO2CH2C2H-μ)2][Co2(CO)6]2 and [p-(HC2CH2OCO)C6H4(CO2CH2C2H-μ)][Co2(CO)6]

The reactions of dipropargyl manolate and terephthalate, respectively, with Co₂(CO)₈ in THF at room temperature gave four new compounds [R(CO₂CH₂C₂H-μ)₂][Co₂(CO)₆]₂ (R=CH₂, 1a; R=C₆H₄, 1b) and [(HC₂CH₂OCO)R(CO₂CH₂C₂H-μ)][Co₂(CO)₆] (R=CH₂, 2a; R=C₆H₄-1,4-, 2b), and compounds 2a and b reacted with RuCo₂(CO)₁₁ to form two new linked clusters [R(CO₂CH₂C₂H-μ)₂][Co₂(CO)₆][RuCo₂(CO)₉] (R=CH₂, 3a; R=C₆H₄-1,4-, 3b). The treatment of two dipropargyl esters, respectively, with RuCo₂(CO)₁₁ afforded another two new clusters [R(CO₂CH₂C₂H-μ)₂][RuCo₂(CO)₉]₂ (R=CH₂, 4a; R=C₆H₄-1,4-, 4b). The reactions of dipropargyl manolate, terephalate with Mo₂Cp₂(CO)₄ gave rise to the formation of dinuclear complexes [(HC₂CH₂OCO)R(CO₂CH₂C₂H-μ)][Mo₂Cp₂(CO)₄] (R=CH₂, 5a; R=C₆H₄-1,4-, 5b), compound 5a reacted with Co₂(CO)₈ to produce the cluster [CH₂(CO₂CH₂C₂H-μ)₂][Co₂(CO)₆][Mo₂Cp₂(CO)₄] 6a. All the new clusters have been characterized by C/H elemental analysis, IR and ¹H NMR spectroscopies. The structure of [CH₂(CO₂CH₂C₂H-μ)₂][Co₂(CO)₆]₂ 1a and [p-(HC₂CH₂OCO)C₆H₄(CO₂CH₂C₂H-μ)][Co₂(CO)₆] 2b have been determined by single crystal X-ray diffraction methods.     

Übergangsmetall-silyl-komplexe: XVII. Synthese von MeCp(CO)2Mn(μ-H)AuPPh3-(Mn-Au) und [MeCp(CO)2Mn(μ-H)]2Pt(3-picolin)2-(Mn-Pt) aus Na[MeCp(CO)2MnSiR3]. Bildung von metall-metall-bindungen bei gleichzeitigem SiR3/H-austausch

Upon reaction of Na[MeCp(CO)₂MnSiR₃] (1) (MeCp = η⁵-CH₃C₅H₄) with Ph₃PAuCl or (3-picoline)₂PtCl₂ (2) in the presence of moist 3-picoline the heteronuclear hydrido complexes MeCp(CO)₂Mn(μ-H)AuPPh₃ (3) or [MeCp(CO)₂Mn(μ-H)]₂Pt(3-picoline)₂ (4) are obtained. In both complexes the hydride ligand bridges the two metals.     

Syntheses and crystal structures of two Zn(II) complexes, [Zn(Fura)2(2,2′-bipy)(H2O)] and [Zn(μ-dnbc)2] (Fura=Furoic acid, 2,2′-bpy=2,2′-bipyridine,dnba=3,5-dinitrobenzoic acid)

Two Zn(II) complexes, [Zn(Fura)₂(2,2′-bpy)(H₂O)] (1) and [Zn(µ-dnbc)₂] (2), have been synthesized and characterized by X-ray diffraction and IR spectra. 1 is a quaternary Zn(II) complex with ZnN₂O₃ configuration distorted square pyramid geometry; 2 is a Zn(II) coordination polymer with 1D double-helical chains bridged by 3,5-dinitrobenzoic acid.     

A new organic–inorganic heteropolyoxometalate compound [Co(2,2′-bipy)3]H[Al(OH)6(Mo6O18)]·17H2O based on B-Anderson–Evans type polyanion (2,2′-bipy=2,2′-bipyridine)

A new organic–inorganic polyoxometalate compound [Co(2,2′-bipy)₃]H[Al(OH)₆ (Mo₆O₁₈)]?·?17H₂O has been synthesized and characterized by elemental analysis, IR, UV spectra, thermogravimetry and differential thermal analysis (TG-DTA) and single-crystal X-ray diffraction analysis. The title compound crystallizes in a monoclinic, C2/c space group, with a?=?37.292(8), b?=?14.214(3), c?=?25.050(5)?Å, β?=?120.62(3), V?=?11426(4)?ų, Z?=?8, F(000)?=?7200, D _c?=?2.116?Mg?m^?3, R?=?0.0748, wR ₂?=?0.1853. Crystal structural analysis indicates that the asymmetric unit in the crystal structure of the title compound consists of one B-Anderson–Evans type heteropolyoxoanion, one octahedral [Co(2,2′-bipy)₃]²⁺ coordination cation, seventeen water molecules of crystallization and a proton based on charge balance. The curves of TG-DTA indicate that weight loss of the title compound is divided into three stages. The third weight loss reveals that the backbone of heteropolyoxoanion decomposes at 744°C.     

Metallkomplexe mit verbrückenden dimethylphosphidoliganden: VI. Zweikernkomplexe mit substituierten vinyldimethylphosphan-brückenliganden durch templatsynthese aus [(C5H5Co)2(μ-PMe2)2(μ-H)]+ und alkinen. Die kristallstruktur von [(C5H5Co)2(μ-PMe2)(μ-η4-Me2PC(CO2Me)CHC(OMe)O)]BF4

The hydrido-bridged dinuclear complex [(C₅H₅CO)₂(μ-PMe₂)₂(μ-H)]BF₄ (I) reacts with C₂(CO₂Me)₂ to produce a mixture of (C₅H₅Co)₂[μ-η⁴-Me₂PC(CO₂Me)C(CO₂Me)PMe₂] (II) and [(C₅H₅Co)₂(μ-PMe₂)(μ-η⁴-Me₂PC(CO₂Me)-CHC(OMe)O)]BF₄ (III). The X-ray structural analysis of III reveals that besides a dimethylphosphido bridge the cation contains a substituted vinyldimethylphosphine ligand which behaves as a 6-electron donor group and is coordinated via phosphorus and oxygen to the first cobalt and via the CC bond the second cobalt atom. The reactions of I with HC₂CO₂Me and CH₃C₂CO₂Me also give mixtures of products which contain the neutral component, (C₅H₅Co)₂[μ-η⁴-Me₂PCRC(CO₂Me)PMe₂] (IV: R  H; VII: R  CH₃), i.e., the structural analogue of II. The ionic products V, VI (obtained from HC₂CO₂Me) and VIII, IX (obtained from CH₃C₂CO₂Me) have been characterized by IR and NMR spectroscopy. {(C₅H₅Co)₂[μ-η⁴-PMe₂C(CH₃)C(CO₂Me)PMe₂](μ-H)}BF₄ (VIII) has independently been prepared by treatment of VII with HBF₄.