Synthesen und Strukturen neuer amido- und imidoverbrückter Cobaltcluster: [Li(THF)2]3[Co3(μ2-NHMes)3Cl6] (1), [Li(DME)3]2[Co18(μ4-NPh)3(μ3-NPh)12Cl3] (2), [Li(DME)3]2[Co6(μ4-NPh)(μ2-NPh)6(PPh2Et)2] (3) und [Li(THF)4][Co8(μ3-NPh)6(μ2-NPh)3(PPh3)2] (4)

Syntheses and Crystal Structures of new Amido- und Imidobridged Cobalt Clusters: [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] (1), [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] (2), [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] (3), and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] (4) The reactions of cobalt(II)-chloride with the lithium-amides LiNHMes and Li₂NPh leads to an amido-bridged multinuclear complex [Li(THF)₂]₃[Co₃(μ₂-NHMes)₃Cl₆] ( 1 ) as well as to the imido-bridged cobalt cluster [Li(DME)₃]₂[Co₁₈(μ₄-NPh)₃(μ₃-NPh)₁₂Cl₃] ( 2 ). In the presence of tertiary phosphines two imido-bridged cobalt clusters [Li(DME)₃]₂[Co₆(μ₄-NPh)(μ₂-NPh)₆(PPh₂Et)₂] ( 3 ) and [Li(THF)₄][Co₈(μ₃-NPh)₆(μ₂-NPh)₃(PPh₃)₂] ( 4 ) result. The structures of 1 – 4 were characterized by X-ray single crystal structure analysis.     

Cyclische Polyselenidoarsenate(III) und -antimonate(III): PPh4[Se5AsSe], PPh4[AsSe6–xSx], (PPh4)2[As2Se6] · 2 CH3CN und (PPh4)2[Se6SbSe]2

Cyclic Polyselenidoarsenates(III) and Polyselenidoantimonates(III): PPh₄[Se₅AsSe], PPh₄[AsSe_6–xS _x ], (PPh₄)₂[As₂Se₆] · 2 CH₃CN, and (PPh₄)₂[Se₆SbSe]₂ In acetonitrile, AsCl₃ and sodiumphenolate formed Cl₂AsOPh which then was reacted with PPh₄Se₅ and finally with Na₂Se to yield PPh₄[Se₅AsSe]. With Na₂S instead of Na₂Se, PPh₄[AsSe_6–xS_x] was obtained; the sulfur contents increased with increasing reaction temperature and time (x = 0.21 to 1.09). With PPh₄Se₂ instead of PPh₄Se₅, (PPh₄)₂[1,4-As₂Se₆] · 2 CH₃CN and PPh₄[Se₅AsSe] were the products. With SbCl₃ instead of AsCl₃, (PPh₄)₂[Se₆SbSe]₂ formed. PPh₄[Se₅AsSe] can also be produced from As₂Se₃, PPh₄Br, Na₂Se and selenium in acetonitrile. The crystal structure of PPh₄[SeAsSe₅] is isotypic with PPh₄[S₅AsS] (X-ray structure analysis with 2414 observed reflexions, R = 0.038). The Se₅AsSe^– ion consists of a six-membered AsSe₅ ring in chair conformation, and the As atom has an additional terminal Se atom. The compounds PPh₄[AsSe_6–xS_x] have the same crystal structures, with sulfur atoms taking all selenium positions at random, but with a preference for the terminal position. The anion in (PPh₄)₂[As₂Se₆] · 2 CH₃CN also has a six-membered ring structure in chair conformation, with two arsenic atoms in positions 1 and 4. The centrosymmetric anion in (PPh₄)₂[Se₆SbSe]₂ consists of a central Sb₂Se₂ ring, and a Se₆ ligand is bonded in a chelating manner to each Sb atom (X-ray structure analysis with 2669 observed reflexions, R = 0.099). ⁷⁷Se-NMR spectra are reported.     

Synthesen und Kristallstrukturen von [Pd9As8(PPh3)8] und [Pd9Sb6(PPh3)8]

Syntheses and Crystal Structures of [Pd₉As₈(PPh₂)₈] and [Pd₉Sb₆(PPh₃)₈] [PdCl₂(PPh₃)₂] reacts with As(SiMe₃)₃ to give the new cluster [Pd₉As₈(PPh₃)₈] ( 4 ). 4 has been characterized by X-ray crystal structure analysis. It is a molecule in which four [Pd₂(PPh₃)₂]-units are bridged by As₂-units. A further Pd atom is located in the centre of the cluster. 4 crystallizes in the space group C2/c with four formula units per unit cell. The lattice constants at 200 K are: a = 3 970.6(3), b = 1 648.90(16), c = 3 266.30(20) pm, β = 131,44(4)°. The reaction of [PdCl₂(PPh₃)₂] with Sb(SiMe₃)₃ yields [Pd₉Sb₆(PPh₃)₈] ( 5 ). 5 consists of a body centred cubic Pd₉-cluster. All of the cube faces are capped by μ₄-Sb-ligands. 5 crystallizes in the space group Pn3 with two formula units per unit cell. The lattice constants at 200 K are: a = b = c = 1 995.4(2) pm.     

Synthese und Kristallstrukturen von [Cu4(As4Ph4)2(PRR′2)4], [Cu14(AsPh)6(SCN)2(PEt2Ph)8], [Cu14(AsPh)6Cl2(PRR′2)8], [Cu12(AsPh)6(PPh3)6], [Cu10(AsPh)4Cl2(PMe3)8], [Cu12(AsSiMe3)6(PRR′2)6] und [Cu8(AsSiMe3)4(PtBu3)4] (R,R′ = organische Gruppen)

Syntheses and Crystal Structures of [Cu₄(As₄Ph₄)₂(PRR′₂)₄], [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈], [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈], [Cu₁₂(AsPh)₆(PPh₃)₆], [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈], [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆], and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] (R, R′ = Organic Groups) Through the reaction of CuSCN with AsPh(SiMe₃)₂ in the presence of tertiary phosphines the compounds [Cu₄(As₄Ph₄)₂(PRR′₂)₄] ( 1 – 3 ) ( 1 : R = R′ = ⁿPr, 2 : R = R′ = Et; 3 : R = Me, R′ = ⁿPr) and [Cu₁₄(AsPh)₆(SCN)₂(PEt₂Ph)₈] ( 4 ) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu₁₄(AsPh)₆Cl₂(PRR′₂)₈] ( 5–6 ) ( 5 : R = R′ = Et; 6 : R = Me, R′ = ⁿPr), [Cu₁₂(AsPh)₆(PPh₃)₆] ( 7 ) and [Cu₁₀(AsPh)₄Cl₂(PMe₃)₈] ( 8 ). Through reactions of CuOAc with As(SiMe₃)₃ in the presence of tertiary phosphines the compounds [Cu₁₂(AsSiMe₃)₆(PRR′₂)₆] ( 9 – 11 ) ( 9 : R = R′ = Et; 10 : R = Ph, R′ = Et; 11 : R = Et, R′ = Ph) and [Cu₈(AsSiMe₃)₄(P^tBu₃)₄] ( 12 ) can be obtained. In each case the products were characterised by single‐crystal‐X‐ray‐structure‐analyses. As the main structure element 1 – 3 each have two As₄Ph₄^2–‐chains as ligands. In contrast 4 – 12 contain discrete AsR^2–ligands.     

Reaktionen von Zinnchloriden mit Polysulfiden. Die Kristallstrukturen von (PPh4)2[SnCl2(S6)2], (PPh4)2[Sn4Cl4S5(S3)O] und (PPh4)2[SnCl6] · S8 · 2CH3CN

Reaction of Tin Chlorides with Polysulfides. Crystal Structures of (PPh₄)₂[SnCl₂(S₆)₂], (PPh₄)₂[Sn₄Cl₄S₅(S₃)O], and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN . The reaction of PPh₄[SnCl₃] with Na₂S₄ in acetonitrile in the presence of small amounts of water yields (PPh₄)₂[Sn₄Cl₄S₅(S₃)O] and minor amounts of (PPh₄)₂[SnCl₂(S₆)₂], PPh₄Cl · 2S₈ and (PPh₄)₂[SnCl₆]. SnCl₄ is partially reduced by (PPh₄)₂S_x, PPh₄[SnCl₃] and (PPh₄)₂[SnCl₆] · S₈ · 2CH₃CN being produced. According to the X-ray crystal structure determination the [Sn₄Cl₄S₅(S₃)O]^2?-ion consists of an O atom that is coordinated by four Sn atoms which in turn are liked with one another by five single S atoms and one S₃ group. In the [SnCl₂(S₆)₂]^2?-ion the Sn atom is octahedrally coordinated by two Cl atoms in trans arrangement and by two chelating S₆ groups. Octahedral [SnCl₆]^2? ions and S₈ molecules in the crown conformation are present in (PPh₄)₄[SnCl₆] · S₈ · 2CH₃CN.