Metall-Schwefelstickstoff-Verbindungen. 22. S4N3Cl als Ausgangsprodukt zur Herstellung von Komplexen mit dem S3N−-Liganden Die Komplexe [Ph6P2N][Cu3(S3N)2(CN)2]und [Ph4As][(CuS3N)2(CN)]

The reaction of S₄N₃Cl with metal salts leads to complexes containing the S₃N^?chelating ligand, a reaction which proceeds smoothly especially in an alkaline medium. Thus we were able to prepare, by the reaction of CuCN with S₄N₃Cl and [Ph₆P₂N]OH (Ph = phenyl), the salt [Ph₆P₂N][Cu₃(S₃N)₂(CN)₂], a compound in which the anions build a bidimensional network through supplementary Cu - S contact interactions. The salt is monoclinic, space group C2/c, a = 18.960, b = 14.651 and c = 15.400 Å, β = 101.03° and Z = 4. Metal Sulfur Nitrogen Compounds. 22. S₄N₃Cl as a Starting Compound for the Preparation of Complexes Containing the S₃N^? Ligand. Complexes [Ph₆P₂N] [Cu₃(S₃N)₂ (CN)₂] and [Ph₄As] [(CuS₃N)₂ (CN)] In contrast, the reaction of CuN with S₄N₃Cl and [Ph₄As]OH led to the compound [Ph₄As][(CuS₃N)₂(CN)], monoclinic, space group C2/c, a = 18.478, b = 6.405, c = 27.051 Å, β = 119.50°, Z = 4. In the centrosymmetric anion the two Cu(S₃N) groups are linked together by disordered CN^? groups. An additional linkage results from Cu - Cu contact interactions, with d = 2.84 Å.     

Metall-Schwefelstickstoff-Verbindungen. 19. Neue Komplexe von CuI mit dem S3N−-Chelatliganden Darstellung und Struktur von [Ph4As][Cu(S3N)(CN)], [(Ph3P)2N][Cu(S3N)(S7N)] und [Ph4As]2[(S3N)Cu(S2O3)Cu(S3N)]

Metal Sulfur-Nitrogen Compounds. 19. Novel Complexes of Cu^I with the S₃N^? Chelate Ligand. Preparation and Structure of [Ph₄As][Cu(S₃N)(CN)], [(Ph₃P)₂N][Cu(S₃N)(S₇N)], and [Ph₄As]₂[(S₃N)Cu(S₂O₃)Cu(S₃N)] In alkaline media S₇NH reacts with Cu salts to yield different products. With Cu(CN) the ion [Cu(S₃N)(CN)]^? is formed, which was isolated as the [Ph₄As]⁺ salt. The crystals are monoclinic, space group P2₁/c, a = 10.499(5), b = 13.418(6), c = 18.032(8) Å, β = 91.84°(3), Z = 4. Besides the known complex ions [Cu(S₃N)₂]^? and [Cu(S₃N)Cl]^? still some more may be obtained when CuCl₂ is reacted with S₇NH: Under special conditions the S₇N ring is partly preserved, and [Cu(S₃N)(S₇N)]^? is formed. Its sparingly soluble [(Ph₃P)₂N]⁺ salt is monoclinic, space group P2₁/n, a = 9.335(6), b = 30.984(11), c = 15.108(8) Å, β = 102.87°(4), Z = 4. Using a longer reaction time a dinuclear complex [(S₃N)Cu(S₂O₃)Cu(S₃N)]^{? ?} results from the reaction of CuCl₂ with S₇NH. The two Cu atoms are bridged by an S atom of the S₂O₃^{? ?} anion. The [Ph₄As]⁺ salt of the dinuclear complex anion is triclinic, space group P1 , a = 11.226(6), b = 12.423(6), c = 19.000(10) Å, β = 76.47°(4), β = 83.98°(4), γ = 84.71°(4), Z = 2. In all these compounds the coordination of Cu^I is trigonal-planar, the S₃N^? chelate group coordinates the Cu in the usual way by two S atoms.     

Metall-Schwefelstickstoff-Verbindungen. 20. Reaktionsprodukte von PdCl2 und Pd(CN)2 mit S7NH. Darstellung und Struktur der Komplexe [Ph6P2N][Pd(S3N)(S5)] und X[Pd(S3N)(CN)2] (X = [Me4N]+, [Ph4P]+)

Metal Sulfur Nitrogen Compounds. 20. Reaction Products of PdCl₂ and Pd(CN)₂ with S₇NH. Preparation and Structure of the Complexes [Ph₆P₂N][Pd(S₃N)(S₅)] and X[Pd(S₃N)(CN)₂] X = [Me₄N]⁺, [Ph₄P]⁺ With PdCl₂ and [Ph₆P₂N]OH S₇NH forms the complex salt [Ph₆P₂N][Pd(S₃N)(S₅)], which could be isolated in two modifications (α- and β-form). The α-form is triclinic, a = 9.347(4), b = 14.410(8), c = 15.440(11) Å, α = 76.27°(5), β = 77.06°(4), γ = 76.61α(4), Z = 2, space group P1 . The β-form is orthorhombic, a = 9.333(2), b = 17.659(4), c = 23.950(6) Å, Z = 4. The structure of the metal complex is the same in the two modifications. One S₃N^? and one S₅^2? are coordinate as chelate ligands to Pd. From S₇NH, Pd(CN)₂, and XOH X = [(CH₃)₄N]⁺ and [(C₆H₅)₄P]⁺ the salts X[Pd(S₃N)(CN)₂] were formed. The (CH₃)₄N-salt is isomorphous with the analogous Ni compound described earlier, the (C₆H₅)₄P-salt is triclinic, a = 9.372(4), b = 10.202(5), c = 13.638(6) Å, α = 86.36α(4), β = 85.66°(4), γ = 88.71°(4), Z = 2, space group P1 . One S₃N^? chelate ligand and two CN^? ions are bound to Pd. In all these complexes the coordination of Pd is nearly square planar.     

Photochemical reactions of M(CO)6 (M = Cr,Mo, W) with Ph2P(S)P(S)Ph2

New complexes {M(CO)₄[Ph₂P(S)P(S)Ph₂]} (M = Cr, Mo and W), (1a)–(3a), [(1a), M = Cr; (2a), M = Mo; (3a), M = W] and {M₂(CO)₁₀[-Ph₂P(S)P(S)Ph₂]} (M = Cr, Mo, W), [(1b)–(3b) [(1b), M = Cr; (2b), M = Mo; (3b), M = W]] have been prepared by the photochemical reaction of M(CO)₆ with Ph₂P(S)P(S)Ph₂ and characterized by elemental analyses, f.t.-i.r. and ³¹P-(¹H)-n.m.r. spectroscopy and by FAB-mass spectrometry. The spectra suggest cis-chelate bidentate coordination of the ligand in {M(CO)₄[Ph₂P(S)P(S)Ph₂]} and cis-bridging bidentate coordination of the ligand between two metals in (M = Cr, Mo and W).     

Reactions of S4N4 with diphosphines,Ph2P(X)PPh2 (X = NC4H8N,CH2CH2)

Reactions of S₄N₄ with diphosphines, Ph₂P(X)PPh₂ (X = NC₄H₈N, CH₂CH₂) have resulted in the isolation of N₃S₃? NPPh₂(X)Ph₂PN? S₃N₃ (X = NC₄H₈N, CH₂CH₂), (S)PPh₂(CH₂CH₂)Ph₂PN? S₃N₃, and (S)PPh₂NC₄H₈NPh₂P(S) as new compounds. These heterocycles have been characterized by analytical and spectroscopic (IR, UV-VIS, ¹H and ³¹P-NMR, and MS) techniques.     

Kinetics of chloride substitution in [Pt(bpma)Cl]+ and [Pt(gly-met-S,N,N)Cl] complexes by thiourea, nitrites, and iodides

Substitution of chloride in [PtCl(bpma)]⁺ and [PtCl(gly-met-S,N,N)], where bpma is bis(2-pyridylmethyl)amine and gly-met-S,N,N is glycyl-l-methionine, was studied as a function of the entering nucleophile concentration and temperature. Reactions between the platinum(II) complexes and thiourea (TU), iodides (I^?), and nitrites(III) (NO ₂ ^? ) were carried out in aqueous solutions using conventional UV-VIS spectrophotometry. Suitable ionic conditions were reached by an addition of 0.1 M NaClO₄ and 0.01 M NaCl (to suppress hydrolysis). The second-order rate constants, k ₂, for the studied reactions with NO ₂ ^? varied between 0.036–0.038 M^?1 s^?1, and for the reactions with TU between 0.095–1.06 M^?1 s^?1, respectively. The reaction between TU and the [PtCl(bpma)]⁺ ion is ten times faster than that of the [PtCl(gly-met-S,N,N)] complex. An analysis of the activation parameters, ΔH ^≠ and ΔS ^≠, for the selected reactions clearly shows their associative nature.     

Crystal structure of (ethoxycarbonylmethyl)triphenylphosphonium tetrafluoroborate

The crystal structure of (ethoxycarbonylmethyl)triphenylphosphonium tetrafluoroborate, Ph₃P⁺CH₂C(O)OEt · BF ₄ ^? (space group P2₁/n, a = 12.727 Å, b = 13.983 Å, c = 12.833 Å, β = 108.83°, Z = 4) is studied by single-crystal X-ray diffraction. The structure was solved by a direct method and refined by full-matrix least squares in the anisotropic approximation to R = 0.056 by 3200 independent reflections (CAD-4 automated diffractometer, λMoK _α). In the phosphonium cation the P atom has a distorted tetrahedral coordination and the P-C-C=O torsion angle is 14.3°. The tetrahedral anion is slightly disordered over two orientations with site occupancies for all atoms of 0.875 and 0.125. The crystal contains unusual interionic hydrogen bonds of the P⁺-C-H…F-B^? type.     

Syntheses, structural and spectroscopic characterization of novel zinc(II)-bis(trithiocarbimato) complexes and bis(N-methylsulfonyldithiocarbimate)-sulfide

Four zinc(II)-bis(trithiocarbimato) complexes with the general formula A₂[Zn(RSO₂NCS₃)₂] [A = Ph₄P⁺: R = CH₃ (1), 4-CH₃C₆H₄ (2); A = Bu₄N⁺: R = CH₃ (3), 4-CH₃C₆H₄ (4)] were obtained by the reaction of sulfur with the correspondent zinc(II)-bis(dithiocarbimato) complexes. Additionally, the compound (Ph₄P)₂[(CH₃SO₂NCS₂)₂S)] (5) was prepared from the potassium methylsulfonildithiocarbimate by oxidation with iodine. The compounds were characterized by elemental analyses and IR, ¹H NMR and ¹³C NMR spectroscopies. The compounds 4 and 5 were also characterized by X-ray diffraction techniques. The compound 4 crystallizes in the centrosymmetric space group C2/c of the monoclinic system. The Zn(II) is in a distorted tetrahedral environment (ZnS₄) in compound 4, and differ from the coordination mode observed in compound 1, which involves one sulfur and one nitrogen atom of each trithiocarbimate ligand. Compound 5 is the first example of a compound containing a bis(N-alkylsulfonyldithiocarbimate)-sulfide dianion and crystallises in the non-centrosymmetric space group P4₁2₁2 of the tetragonal system.     

Crystal structure of catena-DI(2-thiobarbiturato-O,S)aqualead(II)

The crystal structure of catena-di(μ₂-2-thiobarbiturato-O,S)aqualead(II) C₈H₈N₄O₅S₂Pb (C₄H₄N₂O₂S is 2-thiobarbituric acid, H₂TBA) is determined. Crystallographic data for catena-[Pb(H₂O)(μ₂-HTBA-O,S)₂] are as follows: a = 6.5972(1) Å, b = 9.8917(2) Å, c = 10.0893(2) Å, α = 106.702(1)°, β = 93.395(2)°, γ = 107.48(1)°, V = 593.82(2) ų, space group $P\bar 1$ , Z = 2. The Pb²⁺ ion is linked with six monodentate HTBA^? ligands through two O atoms and four S atoms and also connected with a water molecule. Additionally, there is a shortened Pb-S contact (3.622 Å), given which the complex polyhedron represents a distorted square antiprism. Hydrogen bonds N-H…O and O-H…O form a branched three-dimensional network. The structure is also stabilized by the π-π interaction of heterocyclic HTBA^? ions.     

Preparation and Structural Studies of [Mo(N3S2){R2(0)PNP(S)R2}2]

Abstract

The compounds [Mo(N₃S₂){Ph₂(O)PNP(S)Ph₂}₂] 1 [Mo(N₃S₂){ⁱPr₂(O)PNP(S)ⁱPr₂}₂] 2 have been synthesised by treating [MoCl₃(N₃S₂)] with KN(PPh₂S)₂ or KN(PⁱPr₂S)₂. X–Ray structures of 1 and 2 have been solved. On complexation, the MoN₃S₂ ring remained planar, but the Mo(OPNPS)₂ rings are puckered.     

Metall-Schwefelstickstoff-Verbindungen. 13. Die Reaktion von [Ni(HN2S2)2] mit Basen Salze mit den Anionen [Ni(HN2S2)(N2S2)]− und [Ni(N2S2)2]2−

Metal Sulfur Nitrogen Compounds. 13. Reaction of [Ni(HN₂S₂)₂] with Bases. Salts with the Anions [Ni(HN₂S₂)(N₂S₂)]^? and [Ni(N₂S₂)₂]^2? Whereas the complex [Ni(HN₂S₂)₂] reacts with alcoholic solutions of alkaline hydroxides by double deprotonation to the anion [Ni(N₂S₂)₂]^2?, only one proton is removed by the reaction with strong organic bases like tetraalkylammonium, tetraphenylphosphonium, and tetrphenylarsonium hydroxides. The corresponding salts with the anion [Ni(HN₂S₂)(N₂S₂)]^? are formed. The salts containing the tetramethylammonium, tetraethylammonium, tetra-n-butylammonium and tetraphenylarsonium cations were isolated as rather stable, crystalline solids. The structure of the tetraphenylarsonium salt [Ph₄As][Ni(HN₂S₂)(N₂S₂)] was determined by X-ray structure analysis.     

Reaktionsprodukte von S7NH mit Nickel- und Kupfersalzen Darstellung und Struktur der Komplexe [(CH3)4N][Ni(S3N)(CN)2], [(C6H5)4As][Cu(S3N)2] und [(C6H5)4As][Cu(S3N)CI]

Metal Sulfur Nitrogen Compounds 18. Reaction Products of S₇NH with Nickel and Copper Salts. Preparation and Structures of the Complexes [Ch₃₄N][Ni(S₃N)(CN)₂], [(C₆H₅)₄As][Cu(S₃N)₂], and [(C₆H₅)₄AS][Cu(S₃N)Cl]. In the presence of MOH (M = K, [(CH₃)₄N]), S₇NH reacts with Ni(CN)₂ to yield, besides the three-nuclear complex M[(S₃NNi)₃S₂], the new mononuclear complex M[Ni(S₃N)(CN)₂]. The [(CH₃)₄N]⁺ salt is monoclinic, C2/m, a = 19.303(9), b =6.941(3), c=16.309(10) Å, β = 144.51⁰(2), Z = 4. The [Ni(S₃N)(CN)₂]- anion is planar, Ni being coordinated by one S₃N^? chelate ligand and by two CN^? ions. From the reaction of CuCI₂, S₇NH, and [Ph₄As]OH result the salts [Ph₄As][Cu(S₃N)₂] or [Ph₄As][Cu(S₃N)Cl], depending on the reaction conditions. [Ph₄As][Cu(S₃N)₂] is triclinic, P&1macr;, a = 7.073(3), b = 11.742(4), c = 16.439(6) Å α = 91.08°(3), β = 99.01°(3), γ = 91.58°(3), Z = 2. Two S₃N^? chelate ligands coordinate to Cu^I in a distorted tetrahedral arrangement. [Ph₄As][Cu(S₃N)Cl] is monoclinic, C2/c, a = 17.174(6), b = 13.650(5), c = 21.783(5) Å β = 100.45°(2), Z = 8. Cu^I is coordinated by one S₃N^? chelate ligand and one C1^?, resulting in a trigonal planar environment.     

First examples of neutral rhenium(V) complexes with a novel semi-rigid ligand containing a P,N,N,S donor atom set: Synthesis,characterisation and crystal structure

A new PN₂S ligand, N-[2-(diphenylphosphino)phenyl]-2-[(S-trityl)acetylamino]ethanamide [Ph-P(Ph₂)N₂S(Trt)], was synthesised and reacted with Re^V precursors. The reaction of both tritylated and detritylated ligands with ReOCl₃(PPh₃)₂ gave the same expected neutral complex [ReO{Ph-P(Ph₂)N₂S}] (4) in good yield. An unexpected neutral and diamagnetic species, [ReN{Ph-P(Ph₂)N₂S(Trt)}] (5), has been isolated during the complexation of the tritylated ligand with ReNCl₂(PPh₃)₂. The complexes, characterized by classical spectroscopic methods and X-ray analysis for 4, are the first examples of neutral semi-rigid-PN₂S rhenium(V) complexes.     

Crystal structure of catena-Bis(2-thiobarbiturato-O,S)diaquacadmium

The crystal structure of catena-bis(2-thiobarbiturato-O,S)diaquacadmium (C₈H₁₀CdN₄O₆S₂) _n (I), [Cd(H₂O)₂(HTBA)₂] _n (C₄H₄N₂O₂S is 2-thiobarbituric acid, H₂TBA) has been determined. The crystals of compound I are triclinic, a = 6.9433(3) Å, b = 7.2257(3) Å, c = 7.4047(3) Å, α = 88.559(2)°, β = 75.346(2)°, γ = 111.687(1)°, V = 331.05(3) ų, space group $P\bar 1$ , Z = 1. The Cd²⁺ ion is coordinated to the two oxygen atoms of water molecules and the two oxygen and two sulfur atoms of four HTBA^? ions at the vertices of an octahedron. Octahedra are linked by bridging μ₂-HTBA^?-O,S ions into infinite chains. Intermolecular hydrogen bonds form infinite chains. The structure is also stabilized by the π-π interaction of HTBA^? ions.     

Selected Reactions on (R)Ph2PN?S3N3 Heterocycles: Exploration of chemical behavior and reactivity

Reactions of (R)Ph₂PN? S₃N₃ heterocycles with olefins such as norbornadiene, norbornene and dicyclopentadiene have yielded different results. Like Ph₃PN? S₃N₃, (R)Ph₂PN? S₃N₃ (R = C₄H₈N? , C₅H₁₀N? , C₆H₁₂N? , CH₃NC₄H₈N? and OC₄H₈N? ) compounds have given the cycloaddition products (R)Ph₂PN? S₃N₃ · C₇H₈ (yield 41 - 62%) with norbornadiene, while norbornene and dicyclopentadiene have not produced the corresponding adducts under identical conditions. With Ph₃PN? S₃N₃ both norbornene and dicyclopentadiene have given the ring expanded heterocycle, 1,5-[Ph₃PN]₂S₄N₄ in ca. 65% yield. The solution phase decomposition studies of (secondary amino) Ph₂PN? S₃N₃ derivatives have lead to the formation of (R)Ph₂PNH₂⁺X^?, while (primary amino) Ph₂PN? S₃N₃ has given Ph₂PS₂N₃ heterocycle in ca. 80% yield. Acid hydrolysis of (R)Ph₂PN? S₃N₃ derivatives has resulted in the isolation of Ph₂P(O)OH in all the cases, where R is an amino group.     

(18-crown-6)potassium tris(thiocyanato)nickelate(II): Synthesis and crystal structure

A new crystalline complex, (18-crown-6)potassium tris(thiocyanato)nickelate(II), [Ni(SCN)₃K(18-crown-6)] _n (I) was synthesized and studied by X-ray diffraction: space group Cmc2₁, a = 14.749, b = 15.045, c = 10.216 Å, Z = 4, direct method, least-squares full-matrix refinement in anisotropic approximation to R = 0.022 on 2214 independent reflection, CAD-4 automated diffractometer, λMoK _α. In crystal structure I, the [Ni(SCN)₃] _n ^? chains are directed along the axis z with the host-guest [K(18-crown-6)]⁺ fragments attached through the weak K-S bonds to the chains at the side. The complex cations and anions lie in crystallographic plane m. The Ni²⁺ cation has a distorted octahedral coordination. The coordination polyhedron of the K⁺ cation is a distorted hexagonal pyramid with six O atoms of the 18-crown-6 ligand in the base and bifurcate axial vertex at the S and S′ atoms of two SCN^? ligands.     

Fragmentation by electron impact ionization and intracluster reactions of size selected (N2H4) n and (OCS) n clusters

The hydrogen-bonded (N₂H₄) _n clusters and the van der Waals (OCS) _n clusters are size selected in a scattering experiment with a He beam up to the cluster sizen=6. By measuring the angular distributions of the scattered clusters the complete fragmentation pattern of electron impact ionization is obtained. For Hydrazine the two main fragment masses are the protonated species (N₂H₄) _n?1H⁺ and with somewhat weaker intensities also the nominal ion mass (N₂H₄) _n ⁺ . The largest intensity is observed for the monomer ion N₂H ₄ ⁺ to which clusters up ton=5 fragment. For carbonylsulfide, completely different results are obtained. Aside from the fragments of the OCS monomer and the van der Waals cluster fragments (OCS) ₂ ⁺ and (OCS) ₃ ⁺ signals at mass S ₂ ⁺ , S ₃ ⁺ and S₂OCS⁺ are detected. This indicates a fast chemical reaction in the cluster according to: S + OCS → CO + S₂ which occurs for clusters of sizen ≥ 2. Peaks at S ₃ ⁺ and S₂OCS⁺ are seen for the first time forn ≥ 5 according to a further reaction of S₂ in the cluster.     

Synthesis and crystal structure of bis(2,2,2-cryptand potassium) tetrakis(isocyanato)cuprate(II)

A new complex compound, bis(2,2,2-cryptand potassium) tetrakis(isocyanato)cuprate(II), 2[K(Crypt-222)]⁺ [Cu(NCS)4]^2? was prepared and its crystal structure was studied by X-ray structural analysis. The structure includes one symmetrically independent complex cation [K(Crypt-222)]⁺ of a guest-host type and independent one half of [Cu(NCS)₄]^2? anion. Through the center of the anion passes crystallographic symmetry axis 2, the approximate point symmetry of the anion is D ₂, while the approximate point symmetry of the complex cation is D ₃. The coordination polyhedron of the [Cu(NCS)₄]^2? anion (four N atoms) conjugated with Cu²⁺ cation is a nonplanar square considerably screwed into a flattened tetrahedron. The K⁺ cation (coordination number 8) of the complex cation [K(Crypt-222)]⁺ is coordinated by all eight heteroatoms (6O + 2N) of the 2,2,2-cryptand ligand, and its coordination polyhedron can be described as bis-basecentered trigonal prism slightly screwed into an anti-prism.     

Energy and polarization dependence of chemi-ionization processes inK(42 P 3/2)−K(42 P 3/2) collisions

Using crossed molecular beams we have investigated ionizing collisions between potassium atoms in their 4² P _3/2-states, leading to the exit channelsK ₂ ⁺ +e ^?,K ⁺+K ^?, andK(4² S _1/2)+K ⁺+e ^?, respectively. Measurements of the total ionization cross section as well as of the cross sections for the individual channels are reported as a function of both the relative collision energy (0.2 to 2.4 eV) and the angle between the electric field vector of the exciting laser light and the relative velocity vector. The results are interpreted in terms of the molecular states of theK ₂ ^* quasi molecule which are involved in the ionization process.