Acetylenic derivatives of metal carbonyls of the triad Fe,Ru, Os—XI Mass spectra of some binuclear complexes

The mass spectra of the following acetylenic derivatives of iron, ruthenium and osmium carbonyls are reported: the iron compounds Fe₂(CO)₆[C₂(C₆H₅)s₂]₂, Fe₂(CO)₆[C₂(CH₃)₂]₂ and Fe₂(CO)₆[C₂(C₂H₅)₂]₂, the ruthenium compounds Ru₂(CO)₆[C₂(C₆H₅)₂]₂, and Ru₂(CO)₆[C₂(CH₃)₂]₂ and the osmium compounds Os₂(CO)₆[C₂(C₆H₅)₂]₂, Os₂(CO)₆[C₂HC₆H₅]₂ and Os₂(CO)₆[C₂(CH₃)₂]₂. Iron compounds exhibit breakdown schemes where binuclear, mononuclear and hydrocarbon ions are present. On the other hand, ruthenium and osmium compounds fragment in a similar way and give rise to singly and doubly charged binuclear ions. Phenylic derivatives of ruthenium and osmium also give weak triply charged ions. The results are discussed in terms of relative strengths of the metal-metal and metal-carbon bonds.     

Synthesis,spectroscopic and structural characterisation of vanadium(IV) and oxovanadium(IV) complexes with arsenic donor ligands

The reaction of o-C₆H₄(AsMe₂)₂ with VCl₄ in anhydrous CCl₄ produces orange eight-coordinate [VCl₄{o-C₆H₄(AsMe₂)₂}₂], whilst in CH₂Cl₂ the product is the brown, six-coordinate [VCl₄{o-C₆H₄(AsMe₂)₂}]. In dilute CH₂Cl₂ solution slow decomposition occurs to form the V^III complex [V₂Cl₆{o-C₆H₄(AsMe₂)₂}₂]. Six-coordination is also found in [VCl₄{MeC(CH₂AsMe₂)₃}] and [VCl₄{Et₃As)₂]. Hydrolysis of these complexes occurs readily to form vanadyl (VO²⁺) species, pure samples of which are obtained by reaction of [VOCl₂(thf)₂(H₂O)] with the arsines to form green [VOCl₂{o-C₆H₄(AsMe₂)₂}], [VOCl₂{MeC(CH₂AsMe₂)₃}(H₂O)] and [VOCl₂(Et₃As)₂]. Green [VOCl₂(o-C₆H₄(PMe₂)₂}] is formed from [VOCl₂(thf)₂(H₂O)] and the ligand. The [VOCl₂{o-C₆H₄(PMe₂)₂}] decomposes in thf solution open to air to form the diphosphine dioxide complex [VO{o-C₆H₄(P(O)Me₂)₂}₂(H₂O)]Cl₂, but in contrast, the products formed from similar treatment of [VCl₄{o-C₆H₄(AsMe₂)₂}_x] or [VOCl₂{o-C₆H₄(AsMe₂)₂}] contain the novel arsenic(V) cation [o-C₆H₄(AsMe₂Cl)(μ-O)(AsMe₂)]⁺. X-ray crystal structures are reported for [V₂Cl₆{o-C₆H₄(AsMe₂)₂}₂], [VO(H₂O){o-C₆H₄(P(O)Me₂)₂}₂]Cl₂, [o-C₆H₄(AsMe₂Cl)(μ-O)(AsMe₂)]Cl·[VO(H₂O)₃Cl₂] and powder neutron diffraction data for [VCl₄{o-C₆H₄(AsMe₂)₂}₂].     

The chemistry of chromyl fluoride III. Reactions with inorganic systems

Reactions of CrO₂F₂ with MF or MF₂ gave the corresponding M₂CrO₂F₄ and MCrO₂F₄ fluorochromates. With the Lewis Acids (SO₃, TaF₅, SbF₅) and (CF₃CO)₂O known and new chromyl compounds [CrO₂(CF₃COO)₂, CrO₂(SO₃F)₂, CrO₂FTaF₆, CrO₂FSbF₆, CrO₂FSb₂F₁₁] were produced. Chromyl fluoride and inorganic salts (CF₃COONa and NaNO₃) produced the following complexes - Na₂CrO₂F₂(CF₃COO)₂ and Na₂CrO₂F₂(NO₃)₂. Unusual solid products were obtained with CrO₂F₂ and NO, NO₂, SO₂.A new method of preparing CrO₂F₂ is also presented.     

Metallation of aliphatic carbon atoms: II,syntheses and characterization of the cyclopalladated complexes of N,N-dimethylneopentylamine

N,N-Dimethylneopentylamine reacts with Pd(MeCO₂)₂ to give a novel trinuclear cyclopalladated complex [Me₂NCH₂CMe₂CH₂Pd(μ-MeCO₂)₂Pd(μ-MeCO₂)₂PdCH₂CMe₂CH₂NMe₂]?-0.5C₆H₆ (I). The reaction of I with PPh₃ affords both trans-[Pd(MeCO₂)₂(PPh₃)₂] (II) and [Pd(CH₂CMe₂CH₂NMe₂)(MeCO₂)(PPh₃)] (III). The reaction of III with LiCl yields a mononuclear cyclopalladated complex, [Pd(CH₂CMe₂CH₂NMe₂)Cl(PPh₃)] (IV).     

Phase ratios in the K2O-V2O4-SO3 system at high sulfur trioxide concentrations

Phase ratios in the three-component oxide system K₂O-V₂O₄-SO₃ in the region of the sulfur trioxide concentrations corresponding to its concentrations in the active component of vanadium catalysts for SO₂ to SO₃ conversion have been studied using powder X-ray diffraction, IR spectroscopy, microscopy, and chemical analysis. Four individual compounds (K₂VO(SO₄)₂, K₂(VO)₂(SO₄)₃, K₂VO(SO₄)₂S₂O₇, and K₂(VO)₂(SO₄)₂S₂O₇) and K₂(VO)₂(SO₄)₂S₂O₇ and VOSO₄-base solid solutions of composition K₂(VO)_2+x (SO₄)_2+x S₂O₇ (0 ≤ x ≤ 1.5) were found in the system. K₂VO(SO₄)S₂O₇ and K₂(VO)₂(SO₄)₂S₂O₇ lose their sulfur trioxide when heated above 350°C under an inert atmosphere, and convert to K₂VO(SO₄)₂ and K₂(VO)₂(SO₄)₃, respectively. This implies that K₂VO(SO₄)₂S₂O₇ and K₂(VO)₂(SO₄)₂S₂O₇, as well as K₂(VO)_2+x (SO₄)_2+x S₂O₇ solid solution, cannot exist in the active component of real industrial catalysts.     

Tartrate der TypenLn 2(H2 T)3·xH2O undLnH5 T 2·xH2O einiger Seltenerdmetalle

The following compounds were isolated and more closely studied by means of thermal analysis, X-ray scattering and IR absorption spectra and determination of solubilities: Pr₂(H₂ T)₃ · 6 H₂O, Nd₂(H₂ T)₃ · 6 H₂O, Sm₂(H₂ T)₃ · 5 H₂O, Gd₂(H₂ T)₃ · 5 H₂O, Tb₂(H₂ T)₃ · 5 H₂O, Dy₂(H₂ T)₃ · 5 H₂O, Ho₂(H₂ T)₃ · 5 H₂O, Er₂(H₂ T)₃ · 5 H₂O, PrH₅ T ₂ · 2 H₂O, NdH₅ T ₂ · 2 H₂O, SmH₅ T ₂ · 2 H₂O, GdH₅ T ₂ · 3 H₂O, TbH₅ T ₂ · 3 H₂O, DyH₅ T ₂ · 3 H₂O, HoH₅ T ₂ · 3 H₂O, ErH₅ T ₂ · 3 H₂O.     

Dimethylphosphinato and dimethylarsinato complexes of Sb(III) and Bi(III) and their chemistry

Abstract  

The reaction of Me₂PO₂H and Me₂AsO₂H with SbCl₃, BiCl₃, and Bi(NO₃)₃·5H₂O gave the complexes Sb(Me₂PO₂)₃, Sb(Me₂AsO₂)₃, (Me₂PO₂)₂Bi-Cl, Bi(Me₂AsO₂)₃, (Me₂PO₂)₂Bi(NO₃), and (Me₂AsO₂)₂Bi(NO₃)·H₂O, respectively. The arsinato complexes did not react with the Lewis bases pyridine, Ph₃P, and Ph₃As in acetone. The compounds Sb(Me₂AsO₂)₃ and (Me₂AsO₂)₂Bi(NO₃)·H₂O reacted to a small extent with nicotinic acid in methanol but Bi(Me₂AsO₂)₃ gave (Me₂AsO₂-BiO) _x in good yields. (Me₂AsO₂)₂Bi(NO₃)·H₂O in methanol quantitatively rearranged to new complexes with the same composition, [(Me₂AsO₂)₂Bi(NO₃)·H₂O]′ and [(Me₂AsO₂)₂Bi(NO₃)·H₂O]″ in the presence of pyridine. With thiophenol in air, Sb(Me₂AsO₂)₃ gave PhSSPh and Me₂As-SPh (1:1 mol ratio), (Me₂AsO₂-SbO) _x and some Sb(Me₂AsO₂)₃ was reformed, Bi(Me₂AsO₂)₃ gave (Me₂AsO₂-BiO) _x , PhSSPh, and Me₂As-SPh (1:0.6 mol ratio), whereas (Me₂AsO₂)₂Bi(NO₃)·H₂O quantitatively gave PhSSPh, thus acting as a catalyst for the air oxidation of thiophenol.     

Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.     

Piperazine Functionalization of C70 for Incorporation into Supramolecular Assemblies

The photochemical reaction of piperazine with C₇₀ produces a mono‐adduct (N(CH₂CH₂)₂NC₇₀) in high yield (67 %) along with three bis‐adducts. These piperazine adducts can combine with various Lewis acids to form crystalline supramolecular aggregates suitable for X‐ray diffraction. The structure of the mono‐adduct was determined from examination of the adduct I₂N(CH₂CH₂)₂NI₂C₇₀ that was formed by reaction of N(CH₂CH₂)₂NC₇₀ with I₂. Crystals of polymeric {Rh₂(O₂CCF₃)₄N(CH₂CH₂)₂NC₇₀}_n?nC₆H₆ that formed from reaction of the mono‐adduct with Rh₂(O₂CCF₃)₄ contain a sinusoidal strand of alternating molecules of N(CH₂CH₂)₂NC₇₀ and Rh₂(O₂CCF₃)₄ connected through Rh?N bonds. Silver nitrate reacts with N(CH₂CH₂)₂NC₇₀ to form black crystals of {(Ag(NO₃))₄(N(CH₂CH₂)₂NC₇₀)₄}_n?7nCH₂Cl₂ that contain parallel, nearly linear chains of alternating (N(CH₂CH₂)₂NC₇₀ molecules and silver ions. Four of these {Ag(NO₃)N(CH₂CH₂)₂NC₇₀}_n chains adopt a structure that resembles a columnar micelle with the ionic silver nitrate portion in the center and the nearly non‐polar C₇₀ cages encircling that core. Of the three bis‐adducts, one was definitively identified through crystallization in the presence of I₂ as ¹²{N(CH₂CH₂)₂N}₂C₇₀ with addends on opposite poles of the C₇₀ cage and a structure with C_2v symmetry. In ¹²{I₂N(CH₂CH₂)₂N}₂C₇₀, individual ¹²{I₂N(CH₂CH₂)₂N}₂C₇₀ units are further connected by secondary I2???N2 interactions to form chains that occur in layers within the crystal. Halogen bond formation between a Lewis base such as a tertiary amine and I₂ is suggested as a method to produce ordered crystals with complex supramolecular structures from substances that are otherwise difficult to crystallize.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

Organotin and tin(IV) derivatives of dimethyldithioarsinic acid

Organotin derivatives of dimethyldithioarsinic (dithocacodylic) acid have been obtained from the appropriate organotin chloride and the sodium salt of the latter. Tin(IV) chloride and NaS₂AsMe₂ · 2 H₂O yielded only two products, namely Cl₂Sn(S₂AsMe₂)₂ and Sn (S₂AsMe₂)₄, regardless of the reagent ratio. Spectroscopic characterization of the compounds (infrared and¹H NMR) provides structural information suggesting that the dimethyldithioarsinato group behaves as monodentate (or anisobidentate) ligand in Me₂Sn(S₂AsMe₂)₂, Bu₂Sn-(S₂AsMe₂)₂ and Cy₃Sn(S₂AsMe₂), as bidentate in Ph₂Sn(S₂AsMe₂)₂, Ph₃Sn(S₂AsMe₂) and Cl₂As(S₂AsMe₂)₂, whereas Sn(S₂AsMe₂)₄ contains both mono- and bidentate ligands, presumably in a six-coordinate structure.     

Über Alkalimetallmanganchalkogenide A2MnX2 mit A K,Rb oder Cs und X S,Se oder Te

Inhaltsübersicht. Die Verbindungen K₂MnS₂, Rb₂MnS₂, Cs₂MnS₂, K₂MnSe₂, Rb₂MnSe₂, Cs₂MnSe₂, K₂MnTe₂, Rb₂MnTe₂ und Cs₂MnTe₂ wurden durch Umsetzungen von Alkalimetall-carbonaten mit Mangan bzw. Mangantellurid in einem mit Chalkogen beladenen Wasserstoffstrom erhalten. Kristallstrukturuntersuchungen an Einkristallen ergaben, daß alle neun Verbindungen isotyp kristallisieren (K₂ZnO₂-Typ, Raumgruppe Ibam). Untersuchungen zum magnetischen Verhalten zeigen antiferromagnetische Kopplungen der Manganionen in den [MnX_4/2^2–]-Ketten, On Alkali Metal Manganese Chalcogenides A₂MnX₂ with A K, Rb, or Cs and X S, Se, or Te The compounds K₂MnS₂, Rb₂MnS₂, Cs₂MnS₂, K₂MnSe₂, Rb₂MnSe₂, Cs₂MnSe₂, K₂MnTe₂, Rb₂MnTe₂, and Cs₂MnTe₂ were synthesized by the reaction of alkali metal carbonates with Mn or MnTe in a stream of hydrogen charged with chalcogen. Structural investigations on single crystals show that all nine compounds crystallize in isotypic atomic arrangements (K₂ZnO₂ type, space group Ibam). The magnetic behaviour indicates antiferromagnetic interactions of the manganese ions within the [MnX_1/2^2–] chains.     

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.     

Synthesis and characterization of organotin complexes with dithiocarbamates and crystal structures of (4‐NCC6H4CH2)2Sn(S2CNEt2)2 and (2‐ClC6H4CH2)2 Sn(Cl)S2CNBz2

Ten organotin derivatives with dithiocarbamates of the formulae (4‐NCC₆H₄CH₂)₂Sn(S₂CNEt₂)₂ (1), (4‐NCC₆H₄CH₂)₂Sn(S₂CNBz₂)₂ (2), (4‐NCC₆H₄CH₂)₂Sn[S₂CN(CH₂CH₂)₂NCH₃]₂ (3), (2‐ClC₆H₄CH₂)₂ Sn(S₂CNEt₂)₂ (4), (2‐ClC₆H₄CH₂)₂Sn(S₂CNBz₂)₂ (5), (4‐NCC₆H₄CH₂)₂Sn(Cl)S₂CNEt₂ (6), (4‐NCC₆H₄CH₂)₂Sn(Cl)S₂CNBz₂ (7), (4‐NCC₆H₄CH₂)₂Sn(Cl)S₂CN(CH₂CH₂)₂NCH₃ (8), (2‐ClC₆H₄CH₂)₂ Sn(Cl)S₂CNEt₂ (9) and (2‐ClC₆H₄CH₂)₂Sn(Cl)S₂CNBz₂ (10) have been prepared. All complexes were characterized by elemental analyses, IR and NMR. The crystal structures of complexes 1 and 10 were determined by X‐ray single crystal diffraction. For complex 1, the central tin atom exists in a skew‐trapezoidal planar geometry defined by two asymmetrically coordinated dithiocarbamate ligands and two 4‐cyanobenzyl groups. In addition, because of the presence of close intermolecular non‐bonded contacts, complex 1 is a weakly‐bridged dimer. In complex 10, the central tin atom is rendered pentacoordinated in a distorted trigonal bipyramidal configuration by coordinating with S atoms derived from the dithiocarbamate ligand. In vitro assays for cytotoxicity against five human tumor cell lines (MCF‐7, EVSA‐T, WiDr, IGROV and M226) furnished the significant toxicities of the title complexes. Copyright © 2006 John Wiley & Sons, Ltd.     

Zur Bildung von Disilylphosphino-Element-Verbindungen des C,Si, P

The Formation of Disilylphosphino-Element Compounds of C, Si, P The reactions of (me₃Si)₂PLi · OR₂ a (OR₂ = 1 monoglyme or 2 THF; me = CH₃) with CH₃Cl, CH₂Cl₂, ClCH₂CH₂Cl and ClCH₂? C₆H₅ give the compounds (me₃Si)₂Pme, (me₃Si)₂P? CH₂? P(Sime₃)₂, (me₃Si)₂P? CH₂CH₂Cl, (me₃Si)₂P? CH₂CH₂? P(Sime₃)₂ and (me₃Si)₂P? CH₂C₆H₅ respectively. In the same manner a reacts with me₂SiCl₂ in a molar ratio 1:1 to (me₃Si)₂P? Sime₂Cl and in a molar ratio 2:1 to (me₃Si)₂P? Sime₂? P(Sime₃)₂ b . The compound b decomposes to [me₃SiP? Sime₂]₂ and (me₃Si)₃P at 220°C. In the reactions of a with ClP(C₆H₅)₂ and ClPme₂ the compounds (me₃Si)₂P? P(C₆H₅)₂ and (me₃Si)₂P? Pme₂, respectively, are obtained. a reacts with HgCl₂ to (me₃Si)₂P? P(Sime₃)₂. (me₃Si)₃P can be cleaved with ClP(C₆H₅)₂ and ClPme₂ yielding (me₃Si)₂P? P(C₆H₅)₂ and (me₃Si)₂P? Pme₂, respectively. The ¹H- and ³¹P-n.m.r. and mass spectroscopic data are reported.     

Oxalate-2-ethanolamine complexes of some bivalent cations (Mn,Co, Ni,Cu, Zn and Cd)

On the refluxing ofM(II) oxalate (M=Mn, Co, Ni, Cu, Zn or Cd) and 2-ethanolamine in chloroform, the following complexes were obtained: MnC₂O₄·HOCH₂CH₂NH₂·H₂O, CoC₂O₄·2HOCH₂CH₂NH₂, Ni₂(C₂O₄)₂·5HOCH₂CH₂NH₂·3H₂O, Cu₂(C₂O₄)₂·5HOCH₂CH₂NH₂, Zn₂(C₂O₄)₂·5HOCH₂CH₂NH₂·2H₂O and Cd₂(C₂O₄)₂·HOCH₂CH₂NH₂·2H₂O. Following the reaction ofM(II) oxalate with 2-ethanolamine in the presence of ethanolammonium oxalate, a compound with the empirical formula ZnC₂O₄·HOCH₂CH₂NH₂·2H₂O¹ was isolated. The complexes were identified by using elemental analysis, X-ray powder diffraction patterns, IR spectra, and thermogravimetric and differential thermal analysis. The IR spectra and X-ray powder diffraction patterns showed that the complexes obtained were not isostructural. Their thermal decompositions, in the temperature interval between 20 and about 900°C, also take place in different ways, mainly through the formation of different amine complexes. The DTA curves exhibit a number of thermal effects.     

Preparation and Characterization of a Cobalt‐Containing Mono‐Phosphine Ligand and its Coordinated Molybdenum Complex

A cobalt‐containing monodentate phosphine [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(i‐Pr)₂] 2f , was prepared from the reaction of (μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₆ 1 with PhC≡CP(i‐Pr)₂. It was accompanied by an oxidized compound, [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(=O)(i‐Pr₂)] 2fo during the chromatographic process. Further reaction of 2f with Mo(CO)₆ resulted in the formation of a 2f ‐ligated molybdenum complex 4 , [(μ₂‐PPh₂CH₂PPh₂‐κ²P)Co₂(CO)₄][μ₂‐η²‐PhC≡CP(i‐Pr₂)‐κP]‐Mo(CO)₅.     

Synthesis and thermal decomposition of potassium trioxalatoaluminate hydrate

The preparation of pure K₃Al(C₂O₄)₃·mH₂O (2<m<3) is described. Dependent on the mode of preparation, the following were found to be contaminants of the desired product: K₂C₂O₄·1H₂O; KHC₂O₄; KHC₂O₄·H₂C₂O₄·2H₂O; H₂C₂O₄·2H₂O; different forms of aluminium oxide hydrate; K₄Al₂(OH)₂(C₂O₄)₄· (2+x)H₂O (0.7<x<1.7) and K₂Al₂(H₂O)₂(C₂O₄)₄· 4H₂O.     

Bis(cyclopentadienyl)methan-verbrückte Zweikernkomplexe: II. Synthese und Reaktionen ringverbrückter Cobalt-Zweikernkomplexe mit zwei nucleophilen Metallzentren

The dinuclear cobalt complex [CH₂(C₅H₄)₂][Co(PMe₃)₂]₂ (2), which is prepared from CoCl(PMe₃)₃ and [CH₂(C₅H₄)₂]Li₂, reacts with NH₄PF₆ and CH₃I to form the protonated and methylated dications {[CH₂(C₅H₄)₂][CoR(PMe₃)₂]₂}²⁺ (R = H, CH₃). Treatment of {[CH₂(C₅H₄)₂][CoCH₃(PMe₃)₂]₂}I₂ (4) with LiCH₃ affords the neutral compound [CH₂(C₅H₄)₂][Co(CH₃)₂(PMe₃)]₂ (5). Ligand substitution of [CH₂(C₅H₄)₂][Co(CO)₂]₂ (6) with P₂Me₄ and 1,2-C₂H₄(PMe₂)₂(dmpe) gives the doubly-bridged complexes [CH₂(C₅H₄)₂][Co₂(CO)₂(μ-P₂Me₄)] (7) and [CH₂(C₅H₄)₂][Co₂(CO)₂(μ-dmpe)] (8), respectively. Similarly, [CH₂(C₅H₄)₂][Co-(CO)(PMe₃)]₂ (9) is obtained from the reaction of 6 with PMe₃. Oxidation of 6 with iodine gives [CH₂(C₅H₄)₂][Co(CO)I₂]₂ (11) which is transformed via {[CH₂(C₅H₄)₂][Co(PMe₂H)₃]₂}I₄ (12) into the triply-bridged cobalt(II) complex [CH₂(C₅H₄)₂][CO₂(μ-PMe₂)₂] (13).     

Alternativ-Liganden. III. Koordinatives verhalten von chelatliganden des typs me2XSi(Me2)CH2XMe2 (X  N und/oder P: Me  CH3)

Co-ordinative Properties of Chelating Ligands of the Type Me₂XSi(Me₂)CH₂XMe₂ (X ? N and/or P; Me ? CH₃) The reactions of the ligands L ? Me₂XSi(Me₂)CH₂XMe₂ (X ? N and/or P; Me ? CH₃) with M(CO)₆ and M(CO)₄norbor (norbor ? norbornadiene) (M ? Cr, Mo), respectively, yield derivatives of the types M(CO)₅L, M(CO)₄L, and M(CO)₄L₂, respectively. M(CO)₅L compounds are formed from the hexacarbonyls with Me₂NSiMe₂CH₂PMe₂, whereas the ligand Me₂NSiMe₂CH₂NMe₂ does not afford analogous derivatives under the same conditions. Even on substitution of the diene-ligand in M(CO)₄norbor by Me₂NSiMe₂CH₂PMe₂ the chelate complexes M(CO)₄NMe₂SiMe₂CH₂PMe₂ are not obtained, but the cis-disubstituted products M(CO)₄[PMe₂CH₂SiMe₂NMe₂]₂ with phosphorus acting as donor atom are produced. The ligands Me₂PSiMe₂CH₂XMe₂(X ? N, P) give the chelate complexes M(CO)₄PMe₂SiMe₂CH₂XMe₂ in high yields. The new compounds were identified by analytical and spectroscopic (PMR, IR, mass spectra) methods.