Synthesis and Characterization of Gd2[Pt2(SO4)4(HSO4)2](HSO4)2

Red single crystals of Gd₂[Pt₂(SO₄)₄(HSO₄)₂](HSO₄)₂ (triclinic, , Z = 1, a = 844.02(9), b = 908.50(9), c = 939.49(8) pm, α = 107.73(1)°, β = 112.10(1)°, γ = 103.53(1)°) were obtained by the reaction of [Gd(NO₃)(H₂O)₇][PtCl₆]·4H₂O with sulfuric acid at 320 °C in a sealed glass ampoule. In the crystal structure, Pt₂ dumbbells are coordinated by four chelating sulfate groups and two monodentate hydrogensulfate ions. Two further HSO₄^? ions are not bonded to the Pt₂ dumbbell. The Gd³⁺ ions are eightfold coordinated by oxygen atoms. The IR data of Gd₂[Pt₂(SO₄)₄(HSO₄)₂](HSO₄)₂ are typical for these type of compounds. The thermal decomposition of the compound leads to elemental platinum and Gd₂O₃.     

Sulfate und Hydrogensulfate des Erbiums: Er(HSO4)3-I,Er(HSO4)3-II,Er(SO4)(HSO4) und Er2(SO4)3

Sulfates and Hydrogensulfates of Erbium: Er(HSO₄)₃-I, Er(HSO₄)₃-II, Er(SO₄)(HSO₄), and Er₂(SO₄)₃ Rod shaped light pink crystals of Er(HSO₄)₃-I (orthorhombic, Pbca, a = 1195.0(1) pm, b = 949.30(7) pm, c = 1644.3(1) pm) grow from a solution of Er₂(SO₄)₃ in conc. H₂SO₄ at 250 °C. From slightly diluted solutions (85%) which contain Na₂SO₄, brick shaped light pink crystals of Er(HSO₄)₃-II (monoclinic, P2₁/n, a = 520.00(5) pm, b = 1357.8(1) pm, c = 1233.4(1) pm, β = 92.13(1)°) were obtained at 250 °C and crystals of the same colour of Er(SO₄)(HSO₄) (monoclinic, P2₁/n, a = 545.62(6) pm, b = 1075.6(1) pm, c = 1053.1(1) pm, β = 104.58(1)°) at 60 °C. In both hydrogensulfates, Er³⁺ is surrounded by eight oxygen atoms. In Er(HSO₄)₃-I layers of HSO₄^– groups are connected only via hydrogen bridges, while Er(HSO₄)₃-II consists of a threedimensional polyhedra network. In the crystal structure of Er(SO₄)(HSO₄) Er³⁺ is sevenfold coordinated by oxygen atoms, which belong to four SO₄^2–- and three HSO₄^–-tetrahedra, respectively. The anhydrous sulfate, Er₂(SO₄)₃, cannot be prepared from H₂SO₄ solutions but crystallizes from a NaCl-melt. The coordination number of Er³⁺ in Er₂(SO₄)₃ (orthorhombic, Pbcn, a = 1270.9(1) pm, b = 913.01(7) pm, c = 921.67(7) pm) is six. The octahedral coordinationpolyhedra are connected via all vertices to the SO₄^2–-tetrahedra.     

Syntheses of Trifluoromethanethiolato Platinum(II) Complexes – Crystal Structures of cis‐Pt(SCF3)2(PPh3)2 and trans‐Pt(SCF3)Cl(PPh3)2

Ligand exchange reactions of cis‐PtCl₂(PPh₃)₂ and [NMe₄]SCF₃ in different ratios were studied. Depending on the stoichiometry reactions proceeded with formation of products expected for the chosen ratio, i. e. cis‐Pt(SCF₃)Cl(PPh₃)₂, cis‐Pt(SCF₃)₂(PPh₃)₂, and [NMe₄][Pt(SCF₃)₃(PPh₃)]. Starting from cis‐PtCl₂(MeCN)₂ and [NMe₄]SCF₃ and adding PPh₃ after substitution, product mixtures were dominated by the corresponding trans‐isomers. Results of the single crystal structure analyses of cis‐Pt(SCF₃)₂(PPh₃)₂ and trans‐Pt(SCF₃)Cl(PPh₃)₂ are discussed.     

Solvothermal Synthesis,Crystal Structure and Properties of a New Organic Templated Lanthanum Sulfate [C4N3H16][La(SO4)3(H2O)]

A new organic templated lanthanum sulfate [C₄N₃H₁₆][La(SO₄)₃(H₂O)] ( 1 ) has been solvothermally synthesized by using n‐butanol as solvent. The colorless block crystals were characterized by IR, TGA, ICP, and XRD. The structure was determined by single‐crystal X‐ray diffraction: Monoclinic, P2₁/c, a = 10.8878(19), b = 15.478(3), c = 9.9639(18) Å, β = 114.062(2)°, V=1533.2(5) ų, Z = 4]. Crystal structure analysis shows that the one dimensional chain of 1 consists of the LaO₉ polyhedra and the sulfate groups. Coordination water molecules link adjacent chains by using hydrogen bonds to generate 2D layers, whereas the organic amines are inserted between the layers. The formation of 1 demonstrates that solvents play an important role during the synthesis.     

Two Dieneplatinum Synthetic Reagents,Pt(C6H2F3‐2,4,6)2(cod) and Pt(C6HF4‐2,3,4,5)2(cod)

Reactions of PtCl₂(cod) (cod = cycloocta‐1,5‐diene) with 2,4,6‐trifluoro‐ and 2,3,4,5‐tetrafluoro‐phenyllithium in diethyl ether gives Pt(C₆H₂F₃‐2,4,6)₂(cod) ( 1 ) (monoclinic, P2₁/n, Z = 4, a = 7.141(1), b = 15.002(2), c = 17.071(3) Å, β = 91.37(2)°) and Pt(C₆HF₄‐2,3,4,5)₂(cod) ( 2 ) (triclinic, P 1, Z = 2, a = 10.150(2), b = 10.762(2), c = 10.812(2) Å, α = 63.606(3), β = 63.327(3), γ = 76.496(3)°) respectively, which have two ipso carbon atoms and two double bond midpoint centres in a square planar arrangement, and aromatic rings angled near perpendicular to the coordination plane.     

Molekülstruktur und thermische Stabilität des metallacyclischen Platin(II)‐Komplexes [Li(TMEDA)]2Pt(CH2CMe2CMe2CH2)2

Molecular Structure and Thermal Stability of the Metallacyclic Platinum(II) Complex [Li(TMEDA)]₂Pt(CH₂CMe₂CMe₂CH₂)₂ The X‐ray investigation at the “ate‐complex” [Li(TMEDA)]₂Pt(CH₂CMe₂CMe₂CH₂)₂ ( 1 ) revealed a new structure type of homoleptic organometallic compounds of platinum(II). Differences of the molecular structure of the “ate‐complex” [Li(TMEDA)]₂Pt(CH₂CH₂CH₂CH₂)₂ ( 2 ) as well as similarities to the structure of the homologeous “ate‐complex” of nickel(II) [Li(TMEDA)]₂Ni(CH₂CMe₂CMe₂CH₂)₂ ( 3 ) are described. A possible mechanism of the thermal decomposition of the complex 1 is discussed.     

Synthese und Struktur neuer Natriumhydrogensulfate Na(H3O)(HSO4)2; Na2(HSO4)2(H2SO4) und Na(HSO4)(H2SO4)2

Synthesis and Structure of New Sodium Hydrogen Sulfates Na(H₃O)(HSO₄)₂, Na₂(HSO₄)₂(H₂SO₄), and Na(HSO₄)(H₂SO₄)₂ Three acidic sodium sulfates have been synthesized from the system sodium sulfate/sulfuric acid and have been crystallographically characterized. Na(H₃O)(HSO₄)₂ ( A ) crystallizes in the space group P2₁/c with the unit cell parameters a = 6.974(2), b = 13.086(2), c = 8.080(3) Å, α = 105.90(4)°, V = 709.1 Å3, Z = 4. Na₂(HSO₄)₂(H₂SO₄) ( B ) is orthorhombic (space group Pna2₁) with the unit cell parameters a = 9.970(2), b = 6.951(1), c = 13.949(3) Å, V = 966.7 ų and Z = 4. Na(HSO₄)(H₂SO₄)₂ ( C ) crystallizes in the triclinic space group P1 with the unit cell parameters a = 5.084(1), b = 8.746(1), c = 11.765(3) Å, α = 68.86(2)°, β = 88.44(2)°, γ = 88.97(2)°, V = 487.8 Å3 and Z = 2. All three compounds contain SO₄ tetrahedra as HSO₄^? anions and additionally in B and C in form of H₂SO₄ molecules. The ratio H:SO₄ determines the connectivity degree in the hydrogen bond system. In A , there are zigzag chains and dimers additionally connected via oxonium ions. Complex chains consisting of cyclic trimers (two HSO₄^? and one H₂SO₄) are present in B . In structure C , several parallel chains are connected to columns due to the greater content of H₂SO₄. Sodium cations show a distorted octahedral coordination by oxygen in all three structures, the NaO₆ octahedra being “isolated” (connected via SO₄ tetrahedra only) in A . Pairs of octahedra with common edge form Na₂O₁₀ dimeric units in C . Such double octahedra are connected via common corners forming zigzag chains in B .     

Die Kristallstrukturen der Azido‐Platinate (AsPh4)2[Pt(N3)4] und (AsPh4)2[Pt(N3)6]

Crystal Structures of the Azido Platinates (AsPh₄)₂[Pt(N₃)₄] and (AsPh₄)₂[Pt(N₃)₆] The crystal structures of the two homoleptic azido platinates (AsPh₄)₂[Pt(N₃)₄] ( 1 ) and (AsPh₄)₂[Pt(N₃)₆] ( 2 ) were determined by X‐ray diffraction at single crystals. In 1 the [Pt(N₃)₄]^2– ions are without crystallographic site‐symmetry, and the platinum atoms show a planar surrounding. The [Pt(N₃)₆]^2– ions in 2 are centrosymmetric (C_i) with an octahedral surrounding at the platinum atoms. While 1 is highly explosive, 2 is of significantly greater stability. This behaviour is explained by the packing conditions. 1 : Space group P2₁/n, Z = 6, lattice dimensions at –80 °C: a = 1045.3(1), b = 1620.2(1), c = 4041.0(3) pm; β = 96.70(1)°; R₁ = 0.0654. 2 : Space group P1, Z = 1, lattice dimenstions at –80 °C: a = 1027.6(1), b = 1049.1(2), c = 1249.9(3) pm; α = 88.27(1)°, β = 74.13(1)°, γ = 67.90(1)°; R₁ = 0.0417.     

Synthese und Kristallstruktur von Hydrogensulfaten einwertiger Metalle – Ag(H3O)(HSO4)2, Ag2(HSO4)2(H2SO4), AgHSO4 und Hg2(HSO4)2

Synthesis and Crystal Structure of Metal(I) Hydrogen Sulfates – Ag(H₃O)(HSO₄)₂, Ag₂(HSO₄)₂(H₂SO₄), AgHSO₄, and Hg₂(HSO₄)₂ Hydrogen sulfates Ag(H₃O)(HSO₄)₂, Ag₂(HSO₄)₂ · (H₂SO₄), and AgHSO₄ have been synthesized from Ag₂SO₄ and sulfuric acid. Hg₂(HSO₄)₂ was obtained from metallic mercury and 96% sulfuric acid as starting materials. The compounds were characterized by X‐ray single crystal structure determination. Ag(H₃O)(HSO₄)₂ belongs to the structure type of Na(H₃O)(HSO₄). The silver atom is coordinated by 6 + 2 oxygen atoms. In the structure, there are dimers and chains of hydrogen bonded HSO₄^– tetrahedra. Dimers and chains are connected by the H₃O⁺ ion to form a three dimensional hydrogen network. Ag₂(HSO₄)₂(H₂SO₄) crystallizes isotypic to Na₂(HSO₄)₂(H₂SO₄). The coordination number of silver is 6 + 1. The structure of Ag₂(HSO₄)₂(H₂SO₄) is characterized by hydrogen bonded trimers of HSO₄^– tetrahedra, which are further connected to chains. For the recently published structure of AgHSO₄ the hydrogen bonding system was discussed. There are tetrameres and chains, connected by bifurcated hydrogen bonds. The structure of Hg₂(HSO₄)₂ contains Hg₂²⁺ cations with Hg–Hg distance of 2.509 Å. Every mercury atom is coordinated by one oxygen atom at shorter distance (2.18 Å) and three ones at longer distances (2.57 to 3.08 Å). The HSO₄^– tetrahedra form zigzag chains by hydrogen bonds.     

Platinum silicon antimonide (PtSiSb)

Platinum silicon antimonide (PtSiSb) was obtained as a byproduct of a reaction of Pt and Sb in a silica tube. Its structure was determined from X-ray diffraction data (orthorhombic, space group Pbca, Z=8, a=6.3128(8) Å, b=6.3347(8) Å, c=11.3945(12) Å). PtSiSb is closely related to PtSiTe, which adopts a ternary ordered pararammelsbergite (α-NiAs₂)-type structure. The structure of PtSiSb consists of a three-dimensional network built up by condensing PtSi₃Sb₃ octahedra through both corner- and edge-sharing. As in all representatives of the parent α-NiAs₂-type structure, anion-anion pairs are present in PtSiSb. However, the electron count in PtSiSb is 19e⁻ per formula unit, one electron less than that for α-NiAs₂-type structures. This oxidation results in a significant distortion in the PtSiSb structure related to the occurrence of metal-metal pairs. Extended Hückel calculations were carried out on PtSiSb and PtSiTe to analyze these structural transformations as a function of electron count. A narrow band gap (<1 eV) is predicted for PtSiSb; experimental measurements revealed that the resistivity is high (ρ₃₀₀=0.2 Ω cm) and weakly temperature dependent, suggesting a small degree of nonstoichiometry or impurity.     

Structure and Bonding of the Hexameric Platinum(II) Dichloride,Pt6Cl12 (β‐PtCl2)

The crystal structure of Pt₆Cl₁₂ (β‐PtCl₂) was redetermined ( a_h = 13.126Å, c_h = 8.666Å, Z = 3; a_rh = 8.110Å, α = 108.04°; 367 hkl, R = 0.032). As has been shown earlier, the structure is in principle a hierarchical variant of the cubic structure type of tungsten (bcc), which atoms are replaced by the hexameric Pt₆Cl₁₂ molecules. Due to the 60° rotation of the cuboctahedral clusters about one of the trigonal axes, the symmetry is reduced from to ( ). The molecule Pt₆Cl₁₂ shows the (trigonally elongated) structure of the classic M₆X₁₂ cluster compounds with (distorted) square‐planar PtCl₄ fragments, however without metal‐metal bonds. The Pt atoms are shifted outside the Cl₁₂ cuboctahedron by Δ = +0.046Å ( (Pt—Cl) = 2.315Å; (Pt—Pt) = 3.339Å). The scalar relativistic DFT calculations results in the full symmetry for the optimized structure of the isolated molecule with d(Pt—Cl) = 2.381Å, d(Pt—Pt) = 3.468Å and Δ = +0.072Å. The electron distribution of the Pt‐Pt antibonding HOMO exhibits an outwards‐directed asymmetry perpendicular to the PtCl₄ fragments, that plays the decisive role for the cluster packing in the crystal. A comparative study of the Electron Localization Function with the hypothetical trans‐(Nb₂Zr₄)Cl₁₂ molecule shows the distinct differences between Pt₆Cl₁₂ and clusters with metal‐metal bonding. Due to the characteristic electronic structure, the crystal structure of Pt₆Cl₁₂ in space group is an optimal one, which results from comparison with rhombohedral Zr₆I₁₂ and a cubic bcc arrangement.     

A New Family of Binary Layered Compounds of Platinum with Alkali Metals (A = K,Rb, Cs)

By reacting platinum with alkali metals (A = K, Rb, Cs) a new family of binary alkali metal platinides has been synthesized and characterized by chemical analysis, X‐ray powder diffraction, thermal analysis (DTA and DSC), and magnetic measurements. All three compounds exhibit similar XRD‐patterns with strong reflections that can be indexed on the basis of a rhombohedral crystal system (K_xPt: a = 2.6462(1), c = 17.123(1); Rb_xPt: a = 2.6415(1) Å, c = 17.871(1) Å; Cs_xPt: a = 2.6505(1) Å, c = 18.536(1) Å; x < ½. The a lattice constant is independent on the alkali metal used and of value close to the Pt–Pt distance in NaPt₂ (2.645Å). The c parameter increases monotonically with the growing atomic radius of the alkali metal. The average structure of the alloys consists of cubic close packed layers of platinum atoms with layers of disordered alkali metals in between. For all compounds besides the strong reflections small satellites are observed which cannot be indexed together with the rhombohedral peaks in any rational 3‐dimensional lattice. However, these satellites can be indexed as incommensurate modulations within the ab plane (found propagation vectors k = (0.1011, 0.2506, 0) for Cs_xPt, and k = (0.0168, 0.2785, 0) for Rb_xPt).     

Synthese und Kristallstruktur von K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) und Na(HSO4)(H3PO4)

Synthesis and Crystal Structure of K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄), and Na(HSO₄)(H₃PO₄) Mixed hydrogen sulfate phosphates K₂(HSO₄)(H₂PO₄), K₄(HSO₄)₃(H₂PO₄) and Na(HSO₄)(H₃PO₄) were synthesized and characterized by X‐ray single crystal analysis. In case of K₂(HSO₄)(H₂PO₄) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K₂(HSO₄)(H₂PO₄) (T = 298 K), monoclinic, space group P 2₁/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) ų, Z = 4, R₁ = 0.039; K₄(HSO₄)₃(H₂PO₄) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)ų, Z = 1, R₁ = 0.031; Na(HSO₄)(H₃PO₄) (T = 298 K), monoclinic, space group P 2₁, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) ų, Z = 2, R₁ = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K₂(HSO₄)(H₂PO₄) is characterized by hydrogen bonded chains of mixed H_nS/PO₄^– tetrahedra. In the structure of K₄(HSO₄)₃(H₂PO₄), there are dimers of H_nS/PO₄^– tetrahedra, which are further connected to chains. Additional HSO₄^– tetrahedra are linked to these chains. In the structure of Na(HSO₄)(H₃PO₄) the HSO₄^– tetrahedra and H₃PO₄ molecules form layers by hydrogen bonds.     

Kaliumhydrogensulfat-Dihydrogensulfat,K(HSO4)(H2SO4) – Synthese und Kristallstruktur

Potassium Hydrogensulfate Dihydrogensulfate, K(HSO₄)(H₂SO₄) – Synthesis and Crystal Structure Single crystals with the composition KH₃(SO₄)₂ have been synthesized from the system Potassium sulfate/sulfuric acid. The hitherto crystallographically not investigated compound crystallizes in the monoclinic space group P2₁/c (14) with the unit cell parameters a = 7.654(3), b = 11.473(5) and c = 8.643(3) Å, β = 112.43(3)°, V = 701.6 ų, Z = 4 and D_x = 2.22 g · cm^?3. The structure contains two types of tetrahedra, SO₃(OH) and SO₂(OH)₂. These tetrahedra form tetramers via hydrogen bonds consisting of both, two SO₃(OH) and two SO₂(OH)₂ tetrahedra. The tetramers are linked to each other via hydrogen bonds. Potassium is coordinated by 9 oxygen atoms which belong to both kinds of tetrahedra. These potassium oxygen polyhedra are connected by common faces forming chains running parallel z.     

Darstellung,Kristallstrukturen und Schwingungsspektren von trans‐[Pt(N3)4(ECN)2]2–, E = S,Se

Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N₃)₄(ECN)₂]^2–, E = S, Se By oxidative addition to (n‐Bu₄N)₂[Pt(N₃)₄] with dirhodane in dichloromethane trans‐(n‐Bu₄N)₂[Pt(N₃)₄(SCN)₂] and by ligand exchange of trans(n‐Bu₄N)₂[Pt(N₃)₄I₂] with Pb(SeCN)₂ trans‐(n‐Bu₄N)₂[Pt(N₃)₄(SeCN)₂] are formed. X‐ray structure determinations on single crystals of trans‐(Ph₄P)₂[Pt(N₃)₄(SCN)₂] (triclinic, space group P 1, a = 10.309(3), b = 11.228(2), c = 11.967(2) Å, α = 87.267(13), β = 75.809(16), γ = 65.312(17)°, Z = 1) and trans‐(Ph₄P)₂[Pt(N₃)₄(SeCN)₂] (triclinic, space group P 1, a = 9.1620(10), b = 10.8520(10), c = 12.455(2) Å, α = 90.817(10), β = 102.172(10), γ = 92.994(9)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–S = 2.337, Pt–Se = 2.490 and Pt–N = 2.083 (S), 2.053 Å (Se). The approximate linear Azidoligands with N^α–N^β–N^γ‐angles = 172,1–175,0° are bonded with Pt–N^α–N^β‐angles = 116,7–120,5°. In the vibrational spectra the platinum chalcogen stretching vibrations of trans‐(n‐Bu₄N)₂[Pt(N₃)₄(ECN)₂] are observed at 296 (E = S) and in the range of 186–203 cm^–1 (Se). The platinum azide stretching modes of the complex salts are in the range of 402–425 cm^–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtS) = 1.64, f_d(PtSe) = 1.36, f_d(PtN^α) = 2.33 (S), 2.40 (Se) and f_d(N^αN^β, N^βN^γ) = 12.43 (S), 12.40 mdyn/Å (Se).     

Wasserfreie Sulfate der Selten‐Erd‐Elemente: Synthese und Kristallstruktur von Y2(SO4)3 und Sc2(SO4)3

Anhydrous Sulfates of Rare Earth Elements: Syntheses and Crystal Structures of Y₂(SO₄)₃ and Sc₂(SO₄)₃ The reaction of YCl₃ and Li₂SO₄ in sealed gold ampoules yields colorless single crystals of Y₂(SO₄)₃. According to the X‐ray single crystal determination the compound crystallizes with orthorhombic symmetry (Pbcn, Z = 4, a = 1273.97(13), b = 916.76(9), c = 926.08(7) pm, R_all = 0.0274). The crystal structure is buildt up from [YO₆] octahedra and sulfate tetrahedra connected via all vertices. In the same way [ScO₆] octahedra and sulfate groups are connected in the crystal structure of Sc₂(SO₄)₃ (trigonal, R‐3, Z = 6, a = 870.7(1), c = 2247.0(4) pm, R_all = 0.0255). Single crystals of Sc₂(SO₄)₃ were obtained via crystallisation of powder samples from a NaCl melt. The crystal structures of both compounds are closely related to each other and to the binary sulfides Rh₂S₃ and Lu₂S₃; the structures are the same with the complex SO₄^2– ions replacing the S^2– ions of the sulfides.     

Darstellung,Kristallstrukturen und Schwingungsspektren von trans‐[Pt(N3)4X2]2–, X = Cl,Br, I

Synthesis, Crystal Structures, and Vibrational Spectra of trans ‐[Pt(N₃)₄X₂]^2–, X = Cl, Br, I By oxidative addition to (n‐Bu₄N)₂[Pt(N₃)₄] with the elemental halogens in dichloromethane trans‐(n‐Bu₄N)₂[Pt(N₃)₄X₂], X = Cl, Br, I are formed. X‐ray structure determinations on single crystals of trans‐(Ph₄P)₂[Pt(N₃)₄Cl₂] (triclinic, space group P1, a = 10.352(1), b = 10.438(2), c = 11.890(2) Å, α = 91.808(12), β = 100.676(12), γ = 113.980(10)°, Z = 1), trans‐(Ph₄P)₂[Pt(N₃)₄Br₂] (triclinic, space group P1, a = 10.336(1), b = 10.536(1), c = 12.119(2) Å, α = 91.762(12), β = 101.135(12), γ = 112.867(10)°, Z = 1) and trans‐(Ph₄P)₂[Pt(N₃)₄I₂] (triclinic, space group P1, a = 10.186(2), b = 10.506(2), c = 12.219(2) Å, α = 91.847(16), β = 101.385(14), γ = 111.965(18)°, Z = 1) reveal, that the compounds crystallize isotypically with octahedral centrosymmetric complex anions. The bond lengths are Pt–Cl = 2.324, Pt–Br = 2.472, Pt–I = 2.619 and Pt–N = 2.052–2.122 Å. The approximate linear Azidoligands with N^α–N^β–N^γ‐angles = 172.1–176.8° are bonded with Pt–N^α–N^β‐angles = 116.2–121.9°. In the vibrational spectra the platinum halogen stretching vibrations of trans‐(n‐Bu₄N)₂[Pt(N₃)₄X₂] are observed in the range of 327–337 (X = Cl), at 202 (Br) and in the range of 145–165 cm^–1 (I), respectively. The platinum azide stretching modes of the three complex salts are in the range of 401–421 cm^–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtCl) = 1.90, f_d(PtBr) = 1.64, f_d(PtI) = 1.22, f_d(PtN^α) = 2.20–2.27 and f_d(N^αN^β, N^βN^γ) = 12.44 mdyn/Å.     

Platinum(II) complexes containing the 3,3-dimethylglutarimidate ligand

Reaction of cis-[PtCl₂(PPh₃)₂] with excess 3,3-dimethylglutarimide (dmgH) and sodium chloride in refluxing methanol gives the mono-imidate complex cis-[PtCl(dmg)(PPh₃)₂], which was structurally characterized. The plane of the imidate ligand is approximately perpendicular to the platinum coordination plane which, coupled with restricted rotation about the Pt–N bond, results in inequivalent methyl groups and CH₂ protons of the dmg ligand in the room temperature ¹H NMR spectrum. These observations were corroborated by a theoretical study using density functional theory methods. The analogous bromide complex cis-[PtBr(dmg)(PPh₃)₂] can be prepared by replacing NaCl with NaBr in the reaction mixture.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von cis‐(n‐Bu4N)2[Pt(ECN)2(ox)2], E = S,Se

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of cis‐(n‐Bu₄N)₂[Pt(ECN)₂(ox)₂], E = S, Se By exposure of trans‐(n‐Bu₄N)₂[Pt(ECN)₂(ox)₂], E = S and Se, in dichloromethane cis‐(n‐Bu₄N)₂[Pt(SCN)₂(ox)₂] ( 1 ) and cis‐(n‐Bu₄N)₂[Pt(SeCN)₂(ox)₂] ( 2 ) are formed. The crystal structure of 1 (triclinic, space group P1¯, a = 10.789(1), b = 11.906(1), c = 18.580(1)Å, α = 85.619(10), β = 85.272(10), γ = 75.173(10)°, Z = 2) reveals, that the compound crystallizes as a racemic mixture with C₂ point symmetrical complex anions. The bond lengths in both S′‐Pt‐O^˙ axes are Pt‐S′ = 2.321 and Pt‐O^˙ = 2.048 and in the O‐Pt‐O axis Pt‐O = 2.007Å. The oxalato ligands are nearly plane with O‐C‐C‐O torsion angles of 1.4 — 3.9°. The via S′ bound linear thiocyanate groups are coordinated with Pt‐S′‐C angles of 102.6°. In the vibrational spectra the PtE′ stretching vibrations are observed at 327 — 330 ( 1 ) and 217 — 231 cm^—1 ( 2 ). The PtO^˙ and PtO stretching vibrations are coupled with internal vibrations of the oxalato ligands and appear in the range of 400 — 800 cm^—1. Based on the molecular parameters of the X‐ray determination ( 1 ) and estimated data ( 2 ) the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtS′) = 2.08, f_d(PtSe′) = 1.78, f_d(PtO^˙) = 2.45 ( 1 ) and 2.27 ( 2 ) and f_d(PtO) = 2.65 ( 1 ) and 2.60 mdyn/Å ( 2 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved. The NMR shifts are δ(¹⁹⁵Pt) = 4925.9 ( 1 ), 4783.0 ( 2 ) and δ(⁷⁷Se) = 161.7 ppm with the coupling constant ¹J(SePt) = 366.2 Hz.     

Crystal Structures of (PPh3)2Pd(N3)2, (AsPh3)2Pd(N3)2, (2‐Chloropyridine)2Pd(N3)2, [(AsPh4)2][Pd2(N3)4Cl2], [(PNP)2][Pd(N3)4], [(AsPh4)2][Pt(N3)4] · 2 H2O,and [(AsPh4)2][Pt(N3)6]

The crystal structures of the monomeric palladium(II) azide complexes of the type L₂Pd(N₃)₂ (L = PPh₃ ( 1 ), AsPh₃ ( 2 ), and 2‐chloropyridine ( 3 )), the dimeric [(AsPh₄)₂][Pd₂(N₃)₄Cl₂] ( 4 ), the homoleptic azido palladate [(PNP)₂][Pd(N₃)₄] ( 5 ) and the homoleptic azido platinates [(AsPh₄)₂][Pt(N₃)₄] · 2 H₂O ( 6 ) and [(AsPh₄)₂][Pt(N₃)₆] ( 7 ) were determined by X‐ray diffraction at single crystals. 1 and 2 are isotypic and crystallize in the triclinic space group P1. 1 , 2 and 3 show terminal azide ligands in trans position. In 4 the [Pd₂(N₃)₄Cl₂]^2– anions show end‐on bridging azide groups as well as terminal chlorine atoms and azide ligands. The anions in 5 and 6 show azide ligands in equal positions with almost local C_4h symmetry at the platinum and palladium atom respectively. The metal atoms show a planar surrounding. The [Pt(N₃)₆]^2– anions in 7 are centrosymmetric (idealized S₆ symmetry) with an octahedral surrounding of six nitrogen atoms at the platinum centers.