Polysulfonylamines. CXX. Bis(tetrahydrothiophene‐S)gold(I) benzene‐1,2‐disulfonimidate

Both ions of the title compound, [Au(C₄H₈S)₂](C₆H₄NO₄S₂), display crystallographic twofold symmetry. The Au atom exhibits linear coordination, with Au—S = 2.2948 (14) Å and S—Au—S = 178.47 (9)°. The crystal packing consists of layers of anions connected by C—H?O hydrogen bonds; the cations occupy cavities in these layers and the ions are linked by Au?N contacts of 3.009 (7) Å. Further C—H?O interactions connect the layers.     

Über Chalkogenolate. 179. Kupfer(I)-thioxanthate und Thioxanthatocuprate(I)

On Chalcogenolates. 179. Copper(I) Thioxanthates and Thioxanthatocuprates(I) Copper(I) thioxanthates Cu[S₂C? SR], where R = C₂H₅, ⁿC₄H₉, and CH₂? C₆H₅, have been prepared by two procedures and studied by means of diverse methods. They are soluble in ethanolic and acetonic solutions containing the corresponding [S₂C? SR]^? ions in excess to yield thioxanthatocuprates(I) [Cu_n(S₂C? SR)_n+1]^?. The compounds [(C₆H₅)₄P][Cu_n(S₂C? SC₂H₅)_n+1] with n = 1, 4, 6 have been isolated. The existence of [(C₆H₅)₄P][Cu₄(S₂C? SC₄H₉)₅] and [(C₆H₅)₄P][Cu₆(S₂C? SCH₂? C₆H₅)₇] has been ascertained.     

Über Chalkogenolate. 198. Untersuchungen über Polythiocuprate (I) [Cu(Sx)]− 2. Hydrazinium- und Ethylendiammoniumpolythiocuprate(I)

On Chalcogenolates. 198. Studies on Polythiocuprates(I) [Cu(S_x)]^?. 2. Hydrazinium and Ethylenediammonium Polythiocuprates(I) The red polythiocuprates(I) 1–5 (formulae see ?Inhaltsübersicht”?) have been prepared by reaction of hydrazinium or ethylenediammonium polysulfides with copper(II) salts, dissolved in water, under variable conditions. Their properties are described. In aqueous alkaline media 1–5 decompose into CuS and S; in the presence of carbon disulfide CuS, S_x^2?, and CS₃^2? besides CS₄^2? and S₂CO^2? are formed. The existence of the discreet ion [Cu₂CS₇]^2?, described in literature, was not confirmed. The polythiocuprates(I) 1–5 , dissolved im dimethylformamide, decompose via the radical anion S₃^?. The decomposition of S₃^? has been studied kinetically by means of compound 5 . The half-life of decay of S₃^? is τ_1/2 = 71.5 h at 20°C. The pentathiocuprate(I) 3 reacts with n-butyl chloride to produce the substituted sulfanes (C₄H₉)₂S_x′ where x = 1, 2 and 3.     

Über Reaktionen oxygenierter Kobalt(II)-Komplexe. IX. Oxydative Eigenschaften von Tetrakis(äthylendiamin)-μ-peroxo-μ-hydroxo-dikobalt(III)

Reactions of oxygenated cobalt(II) complexes. IX. Oxidative properties of tetrakis(ethylenediamine)-μ-peroxo-μ-hydroxo-dicobalt(III)

1 VIII s. [1].

[(en)₂Co(O₂, OH)Co(en)₂]³⁺ ( a ) reacts with I^? in acidic aqueous solution according to: Co^III(O₂, OH)Co^III + 21^? + 5H⁺ ? 2Co^III + 3H₂O + I₂. Using I^? in excess first order rate constants are obtained which, to a first approximation, are independent of [I^?]. Comparison with kinetic data of deoxygenation of [(en)₂Co(O₂, OH)Co(en)₂]³⁺ under analogous conditions suggests that both reactions have the same rate determining step. The singly bridged species [(en)₂(H₂O)CoO₂Co(H₂O) (en)₂]⁴⁺ is shown to be the reactive intermediate in the iodide oxidation (Schema 2).     

Trägerfixierte Organometallkomplexe. VI. Charakterisierung und Reaktivität Polysiloxan-gebundener (Ether-phosphan)ruthenium(II)-Komplexe

Supported Organometallic Complexes. VI. Characterization und Reactivity of Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes The ligands PhP(R)CH₂D [R = (CH₃O)₃Si(CH₂)₃; D = CH₂OCH₃ ( 1b ); D = tetrahydrofuryl ( 1c ); D = 1,4-dioxanyl ( 1d )] have been used to synthesize (ether-phosphane)ruthenium(II) complexes, which have been copolymerized with Si(OEt)₄ to yield polysiloxane-bound complexes. The monomers cis,cis,trans-Cl₂Ru(CO)₂(P ～ O)₂ ( 3b ) and HRuCl(CO)(P ～ O)₃ ( 5b ) were treated with NaBH₄ to form cis,cis,trans-H₂Ru(CO)₂(P ～ O)₂ ( 4b ) and H₂Ru(CO)(P ～ O)₃ ( 6b ), respectively (P ～ O = η¹-P coordinated; = η²- coordinated). Addition of Si(OEt)₄ and water leads to a base catalyzed hydrolysis of the silicon alkoxy-functions and a precipitation of the immobilized counterparts 4b ′, 6b ′. The polysiloxane matrix resulting by this new sol gel route has been described under quantitative aspects by ²⁹Si CP-MAS NMR spectroscopy. 4b ′ reacts with carbon monoxide to form Ru(CO)₃(P ～ O)₂ ( 7b ′). Chelated polysiloxane-bound complexes Cl₂Ru( )₂ ( 9c ′, d ′) and Cl₂Ru( )(P ～ O)₂ ( 10b ′, c ′) have been synthesized by the reaction of 1b–c with Cl₂Ru(PPh₃)₃ ( 8 ) followed by a copolymerization with Si(OEt)₄. The polysiloxane-bound complexes 9c ′, d ′ and 10b ′, c ′ react with one equivalent of CO to give Cl₂Ru(CO)( )(P ～ O) ( 12b ′– d ′). Excess CO leads to the all-trans-complexes Cl₂Ru(CO)₂(P ～ O)₂ ( 14b ′– d ′), which are thermally isomerized to cis,cis,trans- 3b ′– d ′. The chemical shift anisotropy of ³¹P in crystalline Cl₂Ru( )₂ ( 9a , R = Ph, D = CH₂OCH₃) has been compared with polysiloxane-bound 9d ′ indicating a non-rigid behavior of the complexes in the matrix.     

Über Chalkogenolate. 184. Bis(thiocarbamoyl)- und Bis(N-methylthiocarbamoyl)sulfane

On Chalcogenolates. 184. Bis(thiocarbamoyl)- and Bis (N-methylthiocarbamoyl)sulfanes The sulfanes (H₂N? CS? )₂S₂ and (CH₃? NH? CS? )₂S_x with x = 1 and 2 have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra. The decomposition of the N-methyl substituted compounds has been studied kinetically at 20°C in ethanolic solution.     

Über Reaktionen oxygenierter Kobalt(II)-Chelate. II. Konfigurationsisomere Oxygenierungsprodukte von Tetraäthylenpentaminkobalt(II)

On oxygenation of alcoholic solutions of tetraethylenepentamine cobalt(II) two isomeric forms of [(tetren)CoO₂Co(tetren)]⁴⁺ are obtained in which the configuration of the pentadentate ligand is either α or β. The binuclear complex can be crystallized as thiocyanate or as perchlorate. Oxygenation at 35° produces the pure α isomer. At lower temperature a mixture of α and β is obtained. The isomers differ slightly in their absorption spectra and their reactivity. The ligand configuration has been elucidated by transforming the perchlorates into the [ZnCl₄]^2? salts of the corresponding mononuclear chelates [Co(tetren)Cl]²⁺. The latter have also been prepared starting from a compound of known configuration according to the literature. The IR. spectra of the α and β forms differ characteristically in the NH stretch bands.     

Hexa­aqua­nickel(II) bis­(hypophosphite)

The structure of hexa­aqua­nickel(II) bis­(hypophosphite), [Ni(H₂O)₆](H₂PO₂)₂, has been determined. The crystals are prismatic. The packing of the Ni and P atoms (not the entire hypophosphite anions) is the same as in the structures of [Co(H₂O)₆](H₂PO₂)₂ and [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂. The Ni^II cations have a pseudo‐face‐centered cubic cell, with cell parameter a 10.216 Å and tetrahedral cavities occupied by P atoms. The Ni^II cation has crystallographically imposed twofold symmetry and has an octahedral coordination sphere consisting of six water O atoms, two of which also lie on the twofold axis. The planes of oppositely coordinated water mol­ecules are in a cross conformation. The geometry of the hypophosphite anion is close to point symmetry mm2. The hypophosphite anions are hydrogen bonded to the coordinated water molecules.     

Übergangsmetallphosphidokomplexe. XII. Diphosphenkomplexe (DRPE)Ni[η2-(PR′)2] und die Struktur von (DCPE)NiP(SiMe3)2

Transition Metal Phosphido Complexes. XII. Diphosphene Complexes (DRPE)Ni[η²-(PR′)₂] and the Structure of (DCPE) NiP (SiMe₃)₂ LiP(SiMe₃)₂ reacts with the complexes (DRPE)NiCl₂ 1 (DRPE = R₂PCH₂CH₂PR₂; R = Et: DEPE a ; R = Cy: DCPE b ; R = Ph: DPPE c ) to form the diphosphene complexes (DRPE)Ni[η²-(PSiMe₃)₂] 5a–c . Using low temperature nmr measurements the monosubstitution products (DRPE)Ni[P(SiMe₃)₂]Cl 2a–c and the disubstitution products (DRPE)Ni[P(SiMe₃)₂]₂ 3a, 3c can be detected as intermediates. From the reaction of 1b the paramagnetic nickel(I) complex (DCPE)NiP(SiMe₃)₂ 4b can be isolated. Reacting 1a, 1b with LiP(SiMe₃)CMe₃ the complexes (DRPE)Ni[P(SiMe₃)CMe₃]Cl 8a, 8b , which are analogous to 2 , and the nickel(0) diphosphine complex (DEPE)Ni[η¹-P(SiMe₃)CMe₃P(SiMe₃)CMe₃] 9a can be detected n.m.r. spectroscopically, but no diphosphene complexes can finally be isolated. The diphosphene complexes (DRPE)Ni[η²(PPh)₂] 10a-c are available from reactions of PhP(SiMe₃)₂with l a - c. MeP(SiMe,), reacts only with 1b to give a diphosphene complex (DCPE)Ni[η²(PMe)₂] 11 b. Reacting [P(SiMe₃)CMe₃]₂ with 1a-c the diphosphene complexes (DRPE)Ni[η²(PCMe₃)₂] 12a-c can be obtained. 4b crystallizes monoclinic in the space group P2Jc with a = 1228.6 pm, b = 2387.1 pm, c = 2621.8 pm, β = 92.16°, and Z = 8 formula units. The nickel atom is nearly planar coordinated by three phosphorus- atoms, the phosphorus atom of the terminal P(SiMe₃)₂ group is pyramidally coordinated. The Ni? P bond distances of the two four-coordinated phosphorus atoms are with 219.2 pm and 220.2 pm only slightly shorter than the corresponding distance of the P-atom of the P(SiMe₃)₂ group with 223.5 pm. N.m.r. and mass spectral data are reported.     

Mehrkernige Kobaltkomplexe. V. Präparative Herstellung von Tetrakis (äthylendiamin)-μ-peroxo-μ-amido- und μ-peroxo-μ-thiocyanatodikobalt (III)-Komplexen ausgehend von Tetrakis (äthylendiamin)bis-(ammin)-μ-peroxo-dikobalt (III)-tetraperchlorat

Polynuclear Cobalt Complexes. V. Preparation of tetrakis (ethylenediamine)-μ-peroxo-μ-amido and μ-peroxo-μ-thiocyanato-dicobalt (III) complexes starting from tetrakis (ethylenediamine)bis-(ammine)-μ-peroxo-dicobalt (III)-tetraperchlorate Racemic tetrakis (ethylenediamine)-μ-peroxo-μ-amido-dicobalt (III) thiocyanate and its corresponding hydroperoxo- and superoxo-complexes have been isolated from [(en)₂(NH₃)Co(O₂)(NH₃)(en)₂](ClO₄)₄. A new binuclear peroxo complex containing thiocyanate as bridging ligand was prepared by the same method. The stretching frequencies of the CN- and CS-group as well as the NCS-bending frequence in the IR. spectrum of [(en)₂Co(O₂, SCN)Co(en)₂](NO₃)₃ suggest that the μ-thiocyanato group is N-bonded (2050, 750, 475 cm^?1). A comparison of IR. spectra of known singly and doubly bridged μ-peroxo complexes is made. Characteristic absorption bands, assignable to ν(O? O) and ν(Co? O) are given.     

Methylenverbindungen von Nichtmetallen. VI. Amide der Methan-bis(phosphonigsäure), -bis(phosphonsäure) und -bis(thiophosphonsäure)

Methylene Compounds of Non-Metals. VI. Amides of Methane-bis(phosphonous Acid), -bis(phosphonic Acid) and -bis(thiophosphonic Acid) Symmetrical- and asymmetrical-substituted amides of methane-bis(phosphonous acid), -bis(phosphonic acid) and -bis(thiophosphonic acid) have been obtained by stepwise aminolysis of the chlorides Cl₂(Z)PCH₂P(Z)Cl₂ ( 1 : Z = electron pair; 7 : Z = S; 13 : Z = O) and the fluoride F₂(S)PCH₂P(S)F₂ 19 with dimethylaminotrimethylsilane. Oxidation reactions of trivalent phosphonous amides with sulfur and dimethylsulfoxide have also been investigated.