Oxopentacyano-complexes of molybdenum(IV) and tungsten(IV) in photolysis of octacyanometalates(IV)

Summary Ligand-field (LF) photolysis of aqueous alkaline solutions of K₄[M(CN)₈] (M = Mo or W) containing KCN produces [MO(CN)₅]^3– species. NaCs₂]MO(CN)₅] was isolated and characterised by u.v.-vis., i.r. and Raman spectroscopy. In addition, the reactions of [MO(OH)(CN)₄]^3– with free CN^– are described and the relations between octa-, penta- and tetra-cyanocomplexes are summarised.     

Zur Bestimmung von Selen(IV), Tellur(IV) und Zinn(IV) als Sulfid

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Die Stromspannungskurven von Zirkonium (IV) und Uran(IV)

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Amperometrische Bestimmung von Vanadium(IV) und Titan(IV)

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Titanocene(IV) and vanadocene(IV) complexes of dicyanomethanidobenzoate

The new titanocene and vanadocene complexes of the non-linear pseudohalides Cp₂Ti(dcmb)₂, Cp₂VCl(dcmb), (η⁵-C₅H₄Me)₂VCl(dcmb) and Cp₂V(dcmb)₂ were prepared by reaction of titanocene dichloride (Cp₂TiCl₂) and vanadocene dichlorides (Cp₂VCl₂, (η⁵-C₅H₄Me)₂VCl₂) with dicyanomethanidobenzoic acid (dcmbH, PhC(OH)C(CN)₂). These reactions have proven that the dcmb ligand could be coordinated to the central metal by oxygen or nitrogen donor atoms. The bonding mode of the dcmb ligand reflects properties of the central metal. The strongly oxophilic titanium(IV) shows the bonding through oxygen atom while bonding through nitrogen atom was observed for less oxophilic vanadium(IV). The bonding fashion of the dcmb ligands was determined by spectroscopic methods. X-ray diffraction analysis was used for the structure determination of the compounds dcmbH·H₂O, Cp₂Ti(dcmb)₂·CH₂Cl₂, (η⁵-C₅H₄Me)₂VCl(dcmb) and [Cp₂V(OC(Ph)C(CN)C(OMe)NH)][dcmb].     

Tellur (IV)

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Dicaesiumhexachloroplutonat (IV)

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Selen (IV)

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Plutonium (IV)

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Uran (IV)

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Mixed ligand titanium(IV) complexes. Chlorobis(dithiocarbamato)bis(methylsalicylato)titanium(IV) andbis(dithiocarbamato)bis(methylsalicylato)titanium(IV)

Summary Dichlorobis(methylsalicylato)titanium(IV) reacts with potassium or amine salts of dialkyl or diaryl dithiocarbamates in 11 and 12 molar ratios in anhydrous benzene (room temperature) or in boiling CH₂Cl₂ to yield mixed ligand complexes: (AcOC₆H₄O)₂ Ti(S₂CNR₂)Cl (1) and (AcOC₆H₄O)₂ Ti(S₂CNR₂)₂ (2), R=Et, n-Pr, n-Bu, cyclo-C₄H₈ and cyclo-C₅H₁₀. These compounds are moisture sensitive and highly soluble in polar solvents. Molecular weight measurement in conjunction with i.r.,¹H and¹³C n.m.r. spectral studies suggest coordination number 7 and 8 around titanium(IV) in (1) and (2) respectively.