Synthese und Struktur von [(Ph3C6H2)Te]2, [(Ph3C6H2)Te(AuPPh3)2]PF6 und [(Ph3C6H2)TeAuI2]2

Synthesis and Structure of [(Ph₃C₆H₂)Te]₂, [(Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ and [(Ph₃C₆H₂)TeAuI₂]₂ [(2,4,6-Ph₃C₆H₂)Te]₂ reacts with Ph₃PAu⁺ to yield [2,4,6-Ph₃C₆H₂TeAuPPh₃₂]PF₆ which can be oxidized by I₂ to form the gold(III) complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂. [(2,4,6-Ph₃C₆H₂)Te]₂ crystallizes in the monoclinic space group P2₁/c with a = 810.6(2); b = 2026.5(5); c = 2260.6(7) pm; β = 99.23(3)° and Z = 4. In the crystal structure the ditelluride exhibits a dihedral angle C11? Te1? Te2? C21 of 66.1(2)°. The distance Te1? Te2 is 269.45(6) pm. In the cation of the triclinic complex [(2,4,6-Ph₃C₆H₂)Te(AuPPh₃)₂]PF₆ (space group P1 ; a = 1197.4(3); b = 1457.2(4); c = 1680.0(6) pm; α = 84.69(3)°; β = 85.11(3)°; γ = 75.54(3)°; Z = 2) a pyramidal skeleton RTeAu₂ with distances Te? Au = 259.2(1) and 257.8(2) pm and Au? Au = 295.3(1) pm is present. [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ crystallizes in the triclinic space group P1 with a = 1086.3(3); b = 1462.9(6); c = 1654.2(2) pm; α = 85.25(2)°; β = 87.44(1)°; γ = 80.90(3)°; Z = 2. In the centrosymmetrical dinuclear complex [(2,4,6-Ph₃C₆H₂)TeAuI₂]₂ the Au atoms exhibit a square-planar coordination by two iodine atoms and two tellurolate ligands. The tellurolate ligands form symmetrical bridges with distances Te? Au = 260.0 pm. The distances Au? I are in the range of 260.3(1) and 263.7(1) pm.     

Synthese und Struktur von [(Ph3PAu)6Co(CO)2](PF6) und [(Ph3PAu)7Co(CO)2](PF6)2

Synthesis and Structure of [(Ph₃PAu)₆Co(CO)₂](PF₆) and [(Ph₃PAu)₇Co(CO)₂](PF₆)₂ By the reaction of (Ph₃PAu)₄Co[(CO)₃]⁺ with OH^? in the presence of excess Ph₃PAuCl the larger cluster cations [(Ph₃PAu)₆Co(CO)₂]⁺ ( 1 ) and [(Ph₃PAu)₇Co(CO)₂]²⁺ ( 2 ) can be built up with 1 being the main product. 1 crystallizes with PF^?₆ as counterion in the monoclinic space group C2/c with a = 3008.3(6); b = 1339.1(2); c = 2909.4(6) pm; β = 103.08(1)°; Z = 4. The inner core of the cluster cation 1 with the symmetry C₂ has the form of a bicapped trigonal bipyramid with the heteroatom in equatorial position, and distances Au? Au between 280.4(1) and 288.4(1) pm and Co? Au between 254.9(1) and 257.1(2) pm. 2 · (PF₆)₂ crystallizes in the triclinic space group P1 with a = 2155.7(1); b = 1720.6(1); c = 3543.6(1) pm; α = 91.89(1)°; β = 97.51(1); γ = 89.92(1)°; Z = 4. The unit cell contains two symmetry independent cluster cations 2 of about the same geometry. The cluster skeleton Au₇Co can be described as fragment of an icosahedron formed by seven gold atoms with the Co atom in its center. The Au? Au distances range from 274.8(3) to 332.6(3) pm, and the Co? Au distances are 256.8(6) to 264.7(5) pm. The bonding in 1 and 2 is discussed.     

[N(PPh3)2]2[{Au3Ag2(C2Ph)6} {Au3Cu2(Cu2Ph)6}]: Co-crystallized pentanuclear bimetallic gold-silver and gold-copper clusters

The X-ray structural study of the reaction product of equimolar amounts of [Au₃Cu₂(C₂Ph)₆]. [{Au(C₂Ph)} _n ], and [Ag(C₂Ph)} _n ] revealed two bimetallic anionic [N(PPh₃)₂] + [Au₃Ag₂(C₂Ph)₆]^– and [N(PPh₃)₂]⁺[Au₃Cu₂ (C₂ Pg)₆] — clusters co-crystallized in one asymmetric unit. Each cluster has trigonal bipyramidal geometry with three gold atoms occupying equatorial planes and two silver or copper atoms in the apical positions. Our earlier conclusion based upon spectroscopic characterization describing the product of be above reaction as trimetallic cluster containing three coinage-metals with an overall composition [Au₃CuAg(C₂Ph)₆]^–, was erroneous.Presented at the 210th ACS Meeting, August 19–24, 1995, Chicago, Illinois.     

Über Polygermane. X. Schwingungsspektren der Homocyclen (Ph2Ge)4, (Ph2Ge)5 und (Ph2Ge)6

On Polygermanes. X. Vibrational Spectra of the Homorings (Ph₂Ge)₄, (Ph₂Ge)₅, and (Ph₂Ge)₆ IR and Raman transitions of the crystalline title compounds are given from 3100 to 100 cm^?1. The spectra are nearly identical above 350 cm^?1. The Ge_n ring vibrations range from 330 to 140 cm^?1 and are unspecifically coupled with mass sensitive phenyl modes. The distribution of the individual values is discussed by means of the intracyclic bond angles determined by X-ray structure analysis.     

Molecular and crystal structures of Ph2P(O)(CH2)2OH and Ph2P(O)CH2(C6H6)OH

The molecular and crystal structures of Ph₂P(O)(CH₂)₂OH and Ph₂P(O)CH₂(C₆H₆)OH have been determined. For the first compound the space group is with unit cell dimensions a=10.505(2), b=13.720(2), c=14.782(3) Å; =72.58(6), =76.95(6), =72.49(6)° for Z=6 (Syntex diffractometer,MoK radiation, 2996 reflections, R=3.2%). The second compound crystallizes in the space group P2₁2₁2₁ with unit cell dimensions a=9.371(3), b=9.014(3), c=18.461(5) Å for Z=4 (DAR-UM diffractometer,CuK radiation, 909 reflections, R=4.9%). In Ph₂P(O)(CH₂)₂OH, three independent molecules differing in structural details are linked by the P=O...O hydrogen bonds (O...H is 1.84, 1.80, and 1.86 Å), to form a chain. In Ph₂P(O)CH₂(C₆H₆)OH, the molecules are joined by pairs of the P=O...H–O bonds (O...H is 1.81 Å) to form 16-membered dimeric associates.Institute of Chemical Physics, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 34, No. 3, pp. 109–118, May–June 1993.Translated by T. Yudanova     

Untersuchungen an Polyhalogeniden. XXII [1]. Dimethyldiphenylammoniumpolyiodide (Me2Ph2N)In mit n = 3, 13/3, 6, 8: Darstellung und strukturelle Charakterisierung eines Triiodids (Me2Ph2N)I3, Tridecaiodids (Me2Ph2N)3I13, Dodecaiodids (Me2Ph2N)2I12 und Hexadecaiodids (Me2Ph2N)2I16

Studies of Polyhalides. 22. On Dimethyldiphenylammoniumpolyiodides (Me₂Ph₂N)I_n with n = 3, 13/3, 6, and 8: Preparation and Crystal Structures of a Triiodide (Me₂Ph₂N)I₃, Tridecaiodide (Me₂Ph₂N)₃I₁₃, Dodecaiodide (Me₂Ph₂N)₂I₁₂, and Hexadecaiodide (Me₂Ph₂N)₂I₁₆ The new compounds [(CH₃)₂(C₆H₅)₂N]I₃, [(CH₃)₂(C₆H₅)₂N]₃I₁₃, [(CH₃)₂(C₆H₅)₂N]₂I₁₂ and [(CH₃)₂(C₆H₅)₂N]₂I₁₆ have been prepared by the reaction of dimethyldiphenylammonium iodide [(CH₃)₂(C₆H₅)₂N]I with iodine I₂ in ethanol. Their crystal structures have been determined by single crystal X-ray diffraction methods. The structure of the triiodide may be described as a layerlike packing of pairs of nearly linear symmetric anions and tetraedral cations. The tridecaiodide forms zig-zag chains of iodide ions and iodine molecules with the iodide ion also weakly coordinated by two pentaiodide groups. The dodecaiodide is built from two pentaiodide-groups, which are bridged by an iodine molecule and connected with secondary bonds forming double chains. The hexadecaiodide ion forms layers built up from two heptaiodide groups and one iodine molecule. Thus the dimethyldiphenylammonium cation stabilizes a unique series of polyiodides of extraordinary composition and structure.     

Synthetic and structural chemistry of hexacobalt cluster compounds II. Preparation and structure of Co6(μ-S)8 (Ph2PCH2P(O)Ph2)6

Co₄(μ₃-S)₈(Ph₂PCH₂sP(O)Ph₂)₆, MW = 3012.5, space group R3 , has the hexagonal parameters, a = 26.764 (10), c = 16.979 (10) Å, V = 10532.8 ų, Z = 3. Mo Ka radiation, λ = 0.71069 Å, Dc = 1.425 g/cm³, μ = 9.94 cm^?3, F(000) = 4650, R = 0.073 and Rw = 0.077 for 1965 observed unique reflections with I > 3σ (I). The molecular structure consists of a distorted octahedral Co₄—core. The Co—Co and Co—S distances fall in the range of 2.805—2.838 and 2.213—2.253 Å, respectively.     

Solvent-free mechanochemical synthesis of two Pt complexes: cis-(Ph3P)2PtCl2 and cis-(Ph3P)2PtCO3

Cis-(Ph3P)2PtCl2 and cis-(Ph3P)2PtCO3 were prepared mechanochemically from solid reactants in the absence of a solvent; cis-(Ph3P)2PtCl2 was obtained in 98% yield after ball-milling of polycrystalline PtCl2 and Ph3P; the mechanically induced solid-state reaction of cis-(Ph3P)2PtCl2 with an excess of anhydrous K2CO3 produced cis-(Ph3P)2PtCO3 in 70% yield; the formation of transition metal complexes as a result of mechanochemical solvent-free reactions has been confirmed by means of solid-state 31P MAS NMR spectroscopy, X-ray powder diffraction and differential thermal analysis.     

Die Kristallstruktur des Oxophosphazens [Ph3PNPPh2NP(O)Ph2]

Crystal Structure of the Oxophosphazene [Ph₃PNPPh₂NP(O)Ph₂] Single crystals of [Ph₃PNPPh₂NP(O)Ph₂] were obtained as a by‐product from the synthesis of [NaNPPh₃]₆ as a result of partial hydrolysis. According to the crystal structure determination the compound forms a molecular structure with a PNPNP chain with PN distances between 155.3(6) and 159.8(5) pm and PNP bond angles of 143.2(4) and 140.7(4)°. Space group P1¯, Z = 2, lattice dimensions at 213 K: a = 922.7(1); b = 1040.1(1); c = 1908.0(1) pm; α = 90.55(1)°; β = 103.01(1)°; γ = 92.87(1)°; R = 0.0859.     

Deprotonation of 1,1′-methylenebis[4-tert-butyl-2-(diphenylphosphino)-benzene] and its analogues: synthesis and crystal structure of {5-But-2-[4-But-2-(Ph2P)C6H3(Ph)CH]C6H3P(Ph)K(OEt2)}2

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The synthesis and crystal structures of two-dimensional coordination polymers of Ph2P(O)-CH2CH2-P(O)Ph2 and Ph2P(O)-C5H3N-P(O)Ph2 with praseodymium

Reactions of Pr(NO3)3 with Ph2P(O)-CH2CH2-P(O)Ph2 and Ph2P(O)-C5H3N-P(O)Ph2 yielded layered network coordination polymers with bidentate ligands spanning the lanthanide atoms in a bridging fashion. The praseodymium cations with "spacer" ligands form two-dimensional building blocks assembling into either square grid or herringbone network.     

Syntheses,crystal structures,and characterizations of two novel cubane-like and double cubane-like molybdenum-copper-sulphur clusters {MoCu3S3(S2COEt)}(O)(Ph3P)3 and {Mo2Cu6S6(SCMe3)2}(O)2(Ph3P)4

Two novel heterometallic cubane-like and double cubane-like clusters, {MoCu₃S₃(S₂COEt)}(O)(Ph₃P)₃ I and {Mo₂Cu₆S₆(SCMe₃)₂}(O)₂(Ph₃P)₄ II, were synthesized by reaction of {MoCu₂S₃}(O)(Ph₃P)₃ with CuS₂COEt and CuSCMe₃, respectively. ClusterI crystallized in the triclinic space group (2) witha=12.766(6) Å,b=22.904(5) Å,c=10.522(3) Å, =99.86(2)°, =109.68(2)°, =86.84(3)°,V=2854(2) ų,Z=2,R=0.049 for 6622 observed reflections (I>5(I)) and 410 variables. ClusterII crystallized in the triclinic space group (2) with dimensionsa=14.212(4) Å,b=14.725(5) Å,c=12.396(8) Å, =110.32(4)°, =90.40(5)°, =62.88(2)°,V=2129(2) ų,Z=1,R=0.039 for 6020 observed reflections (I>3(I)) and 461 variables. ClusterI consists of a neutral cubane-like molecule with the core {MoCu₃S₃(S₂COEt)}²⁺, in which one corner of the cubane-like core is a novel triply bridging bidentate 1,1-dithiolato (xanthate, S₂COEt^–) ligand. ClusterII is a double cubane-like one, in which two cubane-like cores {MoCu₃S₃(SCMe₃)}²⁺ are connected by two Cu-S bonds of the triply bridging monothiolato (SCMe ₃ ^– ) ligand. Two different pathways of unit construction from a small heterometallic cluster {MoCu₂S₃}(O)(Ph₃P)₃ have been outlined. Comparisons of the selected bond lengths and bond angles for the cubane-like core {MoCu₃S₃ X} (X=Cl^–, Br^–, S₂COEt^–, SCMe ₃ ^– ) are given. Spectroscopic properties of the title clusters are also reported.     

Die Kristallstruktur von In(CH2Ph)3

Crystal Structure of In(CH₂Ph)₃ The reaction of InCl₃ with PhCH₂MgCl forms tribenzylindane 1 , precipitating from toluene as pale yellow crystals. The crystal structure shows one dimensional chains of 1 in a zigzag arrangement. The synthesis and characterization of (PhCH₂)₂InCl 2 and PhCH₂InCl₂ 3 is reported.