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.     

Halogenomercurate: Darstellung und Strukturen von [Cu(en)2][Hg2Cl6], [Cu(en)2][Hg2Br6] und [Cu(en)2][HgBr4]

Halomercurates: Syntheses and Crystal Structures of [Cu(en)₂][Hg₂Cl₆], [Cu(en)₂][Hg₂Br₆], and [Cu(en)₂][HgBr₄] Crystals of [Cu(en)₂][Hg₂Cl₆] ( 1 ) have been obtained by layering a solution of Hg(NO₃)₂ and NaCl with a solution of [Cu(en)₂]SO₄. An analogous procedure, using NaBr instead of NaCl, gave crystals of [Cu(en)₂][HgBr₄] ( 3 ). Crystals of [Cu(en)₂][Hg₂Br₆] ( 2 ) were obtained by gel crystallization using the same starting materials as for 3 . The complexes show very low solubility. The dinuclear anions of 1 consist of two nearly planar HgCl₃ units related by a center of symmetry. In 2 infinite anionic chains are present, made up of parallel HgBr₃ units. These units are packed in such a way as to produce a trigonal bipyramidal configuration around the Hg atoms. 3 contains mononuclear deformed tetrahedral [HgBr₄]^2– anions. In all three complexes the packing of the ions is such that halogen atoms of halomercurate anions complete a tetragonal bipyramidal coordination at Cu. The resulting Cu–Halogen distances are 2.924 Å for 1 , 3.036 Å for 2 and 3.085 and 3.119 Å for 3 . 1 : Space group P 1, Z = 1, lattice constants at 20 °C: a = 7.000(2), b = 7.526(2), c = 8.239(2) Å; α = 88.39(2), β = 86.06(2), γ = 86.10(3)°; R₁ = 0.040. 2 : Space group P2₁/c, Z = 2, lattice constants at –50 °C: a = 7.185(1), b = 16.338(2), c = 7.814(1) Å; β = 94.88(2)°; R₁ = 0.033. 3 : Space group P2₁/n, Z = 4, lattice constants at 20 °C: a = 8.055(3), b = 13.101(3), c = 13.814(3) Å; β = 91.24(3)°; R₁ = 0.092.     

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 Molekülstrukturen von [Cu20Ga10Cl4Se23(PEt2Ph)12] und [Cu14In6Se7(iPrSe)18]

Syntheses and Structures of [Cu₂₀Ga₁₀Cl₄Se₂₃(PEt₂Ph)₁₂] and [Cu₁₄In₆Se₇(iPrSe)₁₈] CuCl and GaCl₃ react with Se(SiMe₃)₂ in thf solution to yield in the presence of PEt₂Ph [Cu₂₀Ga₁₀Cl₄Se₂₃(PEt₂Ph)₁₂] ( 1 ). Reaction of CuCl, InCl₃ and TMEDA with iPrSeSiMe₃ in DME results in the crystallisation of [Cu₁₄In₆Se₇(iPrSe)₁₈] ( 2 ). The structures of 1 and 2 were determined by X‐ray single crystal structure analysis and display two new types of molecular clusters formed by the elements of group 11, 13, and 16. However, both cluster structures show no analogy to the structures of the related bulk phases.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2NbCl4 und [Re3N3Cl5(PMe2Ph)6][NbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂NbCl₄ and [Re₃N₃Cl₅(PMe₂Ph)₆][NbCl₆] The reaction of ReNCl₂(PMe₂Ph)₃ with NbCl₅ in toluene yields the trinuclear complexes [(Me₂PhP)₃Cl₂ReN]₂‐ NbCl₄ (1) and [Re₃N₃Cl₅(PMe₂Ph)₆][NbCl₆] ( 2 ). 1 forms triclinic crystals with the composition 1 · 2 C₇H₈ (P 1, a = 1074.5(1), b = 1289.1(2), c = 1299.3(2) pm, α = 85.25(2)°, β = 81.04(2)°, γ = 86.02(1)°, Z = 1). In the centrosymmetric compound 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit NbCl₄ to form an almost linear arrangement Re≡N–Nb–N≡Re. The length of the Re–N triple bonds is 172,2 pm, and the Nb–N distances of 216.0 pm correspond to coordinative single bonds. 2 forms orthorhombic crystals with the space group P2₁2₁2₁ and a = 1286.0(1), b = 2109.2(4), c = 2436.2(3) pm, Z = 4. The three Re atoms are located at the corners of a triangle. They are connected by two asymmetric nitrido bridges and two asymmetric chloro bridges. The weakly bent nitrido bridges (Re–N–Re = 152° and 157°) are characterized by Re–N distances of 169 und 207 pm as well as 171 and 207 pm. Re1, in addition, binds a terminal nitrido ligand with Re1–N1 = 166 pm.     

Synthesen und Kristallstrukturen der chalkogenidoverbrückten Nickelclusterverbindungen [Ni5Se4Cl2(PPhEt2)6], [Ni12Se12(PnPr3)6] und [Ni18S18(PiPr3)6]

Syntheses and Crystal Structures of Chalcogenido‐bridged Nickel Cluster Compounds [Ni₅Se₄Cl₂(PPhEt₂)₆], [Ni₁₂Se₁₂(PⁿPr₃)₆], and [Ni₁₈S₁₈(PⁱPr₃)₆] The reaction of (R)ESiMe₃ (R = SiMe₃, Mes = C₉H₁₁; E = S, Se) with [NiCl₂(PPhEt₂)₂] and [NiCl₂(PR₃)₂] (R = ⁿPr, ⁱPr) gives new chalcogenido‐bridged nickel cluster compounds [Ni₅Se₄Cl₂(PPhEt₂)₆]·2THF ( 1 ), [Ni₁₂Se₁₂(PⁿPr₃)₆]·2THF ( 2 ), and [Ni₁₈S₁₈(PⁱPr₃)₆]·2THF ( 3 ). The structures of these compounds were determined by single crystal X‐ray structural analyses.     

Neue amido‐ und imidoverbrückte Kupferkomplexe – Synthesen und Strukturen von [{Li(OEt2)}2][Cu(NPh2)3], [ClCuN(SnMe3)3], [{CuN(SnMe3)2}4], [Cu16(NH2tBu)12Cl16], [{CuNHtBu}8], [Li(dme)3][Cu6(NHMes)3(NMes)2], [PPh3(C6H4)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}2] und [{Li(dme)3}3][Li(dme)2][Cu12(NPh)8]

New Amido and Imido Bridged Complexes of Copper – Syntheses and Structures of [{Li(OEt₂)}₂][Cu(NPh₂)₃], [ClCuN(SnMe₃)₃], [{CuN(SnMe₃)₂}₄], [Cu₁₆(NH₂^tBu)₁₂Cl₁₆], [{CuNH^tBu}₈], [Li(dme)₃][Cu₆(NHMes)₃(NMes)₂], [PPh₃(C₆H₄)CuNHMes], [{[Li(dme)][Cu(NHMes)(NHPh)]}₂], and [{Li(dme)₃}₃][Li(dme)₂][Cu₁₂(NPh)₈] The reactions of stannylated and lithiated amines with coppersalts (halogenides, thiocyanates) lead to amido and imido bridged complexes which contain one to twelve metal atoms. [{Li(OEt₂)}₂][Cu(NPh₂)₃] ( 1 ) results from the reaction of CuCl with LiNPh₂ in the presence of trimethylphosphine. With N(SnMe₃)₃, CuCl reacts to the donor‐acceptor complex [ClCuN(SnMe₃)₃] ( 2 ) that is transformed into the tetrameric complex [{CuN(SnMe₃)₂}₄] ( 3 ) by thermolysis. 3 can also be obtained by the reaction of LiN(SnMe₃)₂ with Cu(SCN)₂. While terminally bound in 1 , the amido ligand is μ₂‐bridging between copper atoms in compound 3 . The influence of the alkyl amide's leaving group can be seen from a comparison of the reactivity of Me₃SnNH^tBu and LiNH^tBu, respectively. With Me₃SnNH^tBu, CuCl₂ forms the polymeric compound [Cu₁₆(NH₂^tBu)₁₂Cl₁₆] ( 4 ) whereas in the case of LiNH^tBu with both CuCl and CuSCN, the complex [{CuNH^tBu}₈] ( 5 ) is obtained. The latter contains two planar Cu₄N₄‐rings similar to those in 3 . If a mesityl group is introduced at the lithium amide, different products are accessible. Both, CuBr and CuSCN, lead to the formation of [Li(dme)₃][Cu₆(NHMes)₃(NMes)₂] ( 6 ) whose anion consists of a prismatic copper core with μ₂‐bridging amido and μ₃‐bridging imido ligands. In the presence of PPh₄Cl, a mixture of Cu(SCN)₂ and LiNHMes enables an ortho‐metallation reaction that produces [PPh₃(C₆H₄)CuNHMes] ( 7 ). From the reaction of CuSCN with LiNHMes and LiNHPh either the dimeric complex [{[Li(dme)][Cu(NHMes)(NHPh)]}₂] ( 8 ) or the cluster [{Li(dme)₃}₃][Li(dme)₂][Cu₁₂(NPh)₈] ( 9 ) results. The anion in 9 exhibits a cubo‐octahedron of copper atoms μ₃‐bridged by (NPh)^2–‐ligands. The solid state structures of compounds 1 – 9 have been determined by single crystal X‐ray diffraction.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.