Darstellung von Organylquecksilber(II)‐di(methansulfonyl)amiden und Kristallstruktur von Ph–Hg–N(SO2Me)2

Polysulfonylamines. CXXIV. Preparation of Organylmercury(II) Di(methanesulfonyl)amides and Crystal Structure of Ph–Hg–N(SO₂Me)₂ Four N,N‐disulfonylated organylmercury(II) amides R–Hg–N(SO₂Me)₂, where R is Me, ⁱPr, Me₃SiCH₂ or Ph, were obtained on treating the appropriate chlorides RHgCl with AgN(SO₂Me)₂, and characterized by ¹H and ¹³C NMR spectra. In the crystal structure of the phenyl compound (orthorhombic, space group Pbca, Z = 8, X‐ray diffraction at –95 °C), the molecule exhibits a covalent and significantly bent C–Hg–N grouping [bond angle 172.7(3)°; Hg–C 204.0(8), Hg–N 209.1(7) pm]. One sulfonyl oxygen atom forms a short intramolecular Hg…O contact [296.1(5) pm] and simultaneously catenates glide‐plane related molecules via a second Hg…O interaction 297.6(5) pm], thus conferring upon Hg^II the effective coordination number 4 and a geometrically irregular coordination polyhedron (bond angles from 173 to 54°).     

Die Kristall- und Molekülstruktur von (CH3)2SnSAB (SAB = Dianion von 2-Hydroxy-N-(2-hydroxybenzyliden)-anilin)

Crystal and Molecular Structure of (CH₃)₂SnSAB. (SAB = Dianion of 2-Hydroxy-N-(2-hydroxybenzylidene)-aniline) (CH₃)₂SnSAB, C₁₅H₁₅NO₂Sn (SAB = tridentate dianion of 2-hydroxy-N-(2-hydroxybenzylidene)-aniline in SCHIFF base form) crystallizes in the space group Pben (D) with a = 19.271(5), b = 10.508(2), c = 13.379(1) Å and Z = 8. The structure has been solved using 1307 symmetrical independent reflections and applying the heavy atom method; the position of all atoms, except the H atoms, has been determined. As interatomic distances have been found: Sn? C: 2.117(14), Sn? O:2.112(9), Sn? N:2.229(11) N? C 10 (phenyl group II): 1.462(16), C9-N (SCHIFF base bridging group): 1.257(18), C 9? C8 (phenyl group I): 1.441(18) Å; mean C? C distances in the phenyl groups: 1.403(18) Å. Two molecules at a time have a centre of symmetry and weakly coordinate through two loose Sn? O bridges (intermolecular Sn? O distance: 2.881(8) Å). The individual molecules essentially form a distorted trigonal bipyramid with N and both methyl-C atoms in the equatorial plane; ? CSnC = 138.52(50)°; ? OSnO = 158.58(35)°.     

Cyclothiazenokomplexe von Molybdän(V) und (VI), sowie von Wolfram(VI) Die Kristallstruktur von (PPh4)2[MoCl3(N3S2)]2 · 2 CH2Cl2

Cyclothiazeno Complexes of Molybdenum(V), Molybdenum(VI), and Tungsten(VI). Crystal Structure of (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ . From excess trithiazylchloride and molybdenum or tungsten hexacarbonyl, respectively, the cyclothiazeno complexes [MCl₃(N₃S₂)]₂(S₂N₂) are obtained. They possess metal atoms linked via a planar S₂N₂ ring. The corresponding bromo compounds [MBr₃(N₃S₂)]₂(S₂N₂) can be obtained in liquid bromine from S₄N₄ and MoBr₄ or WBr₆, respectively, or from S₄N₄ with the corresponding metal hexacarbonyls in the presence of bromine. Thermolysis of [WBr₃(N₃S₂)]₂(S₂N₂) yields [WBr₃(N₃S₂)]₂ which is dimerized via nitrogen bridges. When [MoCl₃(N₃S₂)]₂(S₂N₂) reacts with tetraphenylphosphonium chloride in dichloromethane, the S₂N₂ acts as reducing agent, and the paramagnetic molybdenum(V) complex (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ is obtained (μ_eff = 1.2 B.M.). The i.r. spectra are reported. The crystal structure of (PPh₄)₂[MoCl₃(N₃S₂)]₂ · 2 CH₂Cl₂ was determined by X-ray diffraction (2524 independent reflexions, R = 0.052). It crystallizes in the space group P1 with the lattice con- stants a = 943.9, b = 1209.6, c = 1469.2 pm, α = 69.27, β = 72.20 and γ = 82.08°, Z = 1. There are tetraphenylphosphonium cations and centrosymmetric, dimeric anions [MoCl₃(N₃S₂)]₂^2?. The molybdenum atoms are part of six-membered cyclothiazeno rings MoN₃S₂ with MoN bond lengths of 177 and 197 pm; the N atom with the longer MoN bond is linked to the second Mo atom, so that a planar Mo₂N₂ ring results; this ring is nearly coplanar with the two MoN₃S₂ rings. Furthermore, each molybdenum atom is linked with three chlorine atoms with MoCl bond lengths of 240–242 pm, so that the Mo atoms possms a distorted octahedral coordination.     

C–H-Aktivierung: Synthese und Eigenschaften von Acetonato(C)acidophthalocyaninato(2–)metallaten(III) von Rhodium und Iridium; Kristallstruktur von Tetra(n-butyl)ammoniumacetonato(C)-azidophthalocyaninato(2–)iridat(III)

C–H-Activation: Syntheses and Properties of Acetonato( C )-acidophthalocyaninato(2–)metallates(III) of Rhodium and Iridium; Crystal Structure of Tetra(n-butyl)ammonium Acetonato( C )azidophthalocyaninato(2–)iridate(III) Phthalocyaninato(2–)metallate(I) of rhodium and iridium reacts with carbonyl substrates like acetone or acetylacetone and halides or pseudohalides forming acetonato(C)- or acetylacetonato(C)acidophthalocyaninato(2–)metallates(III), that are isolated as tetra(n-butyl)ammonium complex salts (ⁿBu₄N)[M(R)(X)pc^2–] (M = Rh, Ir; R = aC, acaC; X = Cl, I, N₃, SCN/NCS). (ⁿBu₄N)[Ir(aC)(N₃)pc^2–] · 0,25(C₂H₅)₂O · 0,5 CH₂Cl₂ crystallizes in the triclinic space group P1 with cell parameters a = 16.267(8) Å, b = 17.938(3) Å, c = 18.335(4) Å, α = 74.77(2)°, β = 73.73(3)°, γ = 84.25(3)°, V = 4954(3) ų, Z = 4. There are two crystallographically independent anions, differing by the orientation of the azido ligand either towards an isoindole group or a N_aza bridge of the phthalocyaninate, while the σ-C bonded acetonate is always oriented towards an isoindole group (gauche and ecliptical configuration). The Ir–C distances are 2.12(1) and 2.14(1) Å. Due to the trans influence of the acetonate-C atom the Ir-azide-N distances of 2.22(1)/2.24(1) Å are longer than expected. The electrochemical properties and the optical, vibrational, and ¹H-NMR spectra are discussed.     

Die Reaktionen von Dimethylsulfoxid mit Molybdäntetrabromid und Molybdändibromid-dinitrosyl Die Kristallstruktur von [MoBr2(NO)2(OSMe2)2]

Reactions of Dimethyl Sulfoxide with Molybdenum Tetrabromide and Molybdenum Dibromide Dinitrosyl. Crystal Structure of [MoBr₂(NO)₂(OSMe₂)₂] In the cold molybdenum tetrabromide reacts with an equivalent amount of dimethyl sulfoxide forming the solvate [MoBr₄(OSMe₂)₂]; excess dimethyl sulfoxide yields [MoO₂Br₂(OSMe₂)₂] which is also obtained by other methods. Molybdenum dibromidedinitrosyl forms the solvate [MoBr₂(NO)₂(OSMe₂)₂] in the reaction with dimethyl sulfoxide. According to the i.r. spectra all complexes display O-coordination of the OSMe₂ molecules. [MoBr₂(NO)₂(OSMe₂)₂] crystallizes monoclinic in the space group P2₁/c with four formula units per unit cell. The cell dimensions are a = 1236, b = 892, c = 1305 pm, β = 95.2°. 1662 independent observed reflexions were used for refinement; R = 3.8%. The molybdenum atoms are six-coordinated, the O atoms of the dimethyl sulfoxide molecules are in trans-position to the nitrosyl ligands, which form linear groups Mo? N? O.     

Darstellung und Eigenschaften von Phthalocyaninato(2–)indaten(III) mit einzähnigen Acido-Liganden; Kristallstruktur von Tetra(n-butyl)ammonium-cis-difluoro-Phthalocyaninato(2–)indat(III)-Hydrat

Preparation and Properties of Phthalocyaninato(2–)indates(III) with Monodentate Acido Ligands; Crystal Structure of Tetra(n-butyl)ammonium cis -Difluorophthalocyaninato(2–)indate(III) Hydrate Tetra(n-butyl)ammonium cis-diacidophthalocyaninato(2–)indates(III) with the monodentate acido ligands fluoride, chloride, cyanide and formiate are synthezised by the reaction of chlorophthalocyaninatoindium(III) or cis-dihydroxophthalocyaninatoindate(III) with the respective tetra(n-butyl)ammonium salt or ammonium formiate and are characterized by their UV/VIS spectra and their vibrational spectra. The difluoro-complex salt crystallizes as a hydrate ((ⁿBu₄N)^cis[In(F)₂pc^2–] · H₂O) in the monoclinic space group P2₁/n (no. 14) with cell parameters: a = 13.081(3) Å, b = 13.936(2) Å, c = 23.972(2) Å; β = 97.79(1)°, Z = 4. Hexa-coordinated indium is surrounded by four isoindole nitrogen atoms (N_iso) and two cis-positioned fluorine atoms. The average In–F and In–N_iso distance are 2.0685(4) and 2.2033(5) Å, respectively, and the F–In–F angle is 81.5(1)°. The In atom is displaced outside the centre (Ct) of the N_iso plane towards the fluoride ligands: d(In–Ct) = 0.953(1) Å. The phthalocyaninato(2–) core is nonplanar (unsymmetrical concave distortion).     

Umlagerungsreaktionen von (2′-Propinyl)cyclohexadienolen und -semibenzolen

Rearrangements of (2′-Propinyl)cyclohexadienols and -semibenzenes The acid-catalyzed dienol-benzene rearrangement of 3- and 5-methyl-substituted (2′-propinyl)cyclohexadienols has been investigated. Treatment of the dienols with CF₃COOH in CCl₄ yields allenyl- and (2′-propinyl)benzenes via [3,4]- and [1,2]-sigmatropic rearrangements, respectively. The reaction with H₂SO₄ in Et₂O leeds to a mixture of allenyl-, 2′-propinyl-, 3′-butinyl- and (2′,3′-butadienyl)benzenes (Scheme 3). The latter are products of a thermal semibenzene-benzene rearrangement (cf. Scheme 9). The corresponding semibenzenes have been prepared by dehydration of the cyclohexadienols with H₂SO₄ or POCl₃ (Schemes 6 and 7). Under acidic conditions, the p-(2′-propinyl)semibenzenes 33–35 (Scheme 8) undergo [3,4]- and [1,2]-sigmatropic rearrangements to give again allenyl- and (2′-propinyl)benzenes, whereas the thermal rearrangements to the 3′-butinyl- and (2′,3′-butadienyl)benzenes (Scheme 9) involves a radical mechanism. In contrast, the o-(2′-propinyl)semibenzene b (Scheme 7) leads to (2′,3′-butadienyl)benzene 32 via a thermal [3,3]-sigmatropic rearrangement.     

Über die Synthese von 2-(p-Biphenylyl)-isopropyloxycarbonyl-(Bpoc)-Aminosäuren und den Zerfall von Aralkyl-phenyl-carbonaten

The syntheses of a number of new Bpoc-amino acids and the preparation of some activated esters of Bpoc-amino acids are described. In recent work on the total synthesis of calcitonin hormones the Bpoc residue has been found to be very useful for the selective protection of α-amino groups of complicated intermediate peptide fragments. The reagent preferentially used for the introduction of the Bpoc group into amino acids, [2-(p-biphenylyl)-isopropyl]-phenyl-carbonate (I), is stable at 0°, but undergoes at higher temperatures a decomposition which is a accelerated by phenol. Based on the reaction products formed — [2-(p-biphenylyl)-isopropyl]-phenyl-ether (II), 2-(p-biphenylyl)-propene (III), and phenol — a scheme is proposed for this thermal decomposition, and the possibility of a correlation between the stability of carbonates R₃C—O—CO—OC₆H₅ and the rate of the acidolytic cleavage of urethanes R₃C—O—CO—NHR′ depending on the substituents R is discussed.     

Dimethylsulfoxid‐Komplexe von Beryllium(II)‐chlorid. Kristallstrukturen von [Be(OSMe2)4]Cl2, [Be(OSMe2)3(H2O)]Cl2 und [Be(OSMe2)2(H2O)2]Cl2

Dimethylsulfoxide Complexes of Beryllium(II) Chloride. Crystal Structures of [Be(OSMe₂)₄]Cl₂, [Be(OSMe₂)₃(H₂O)]Cl₂ and [Be(OSMe₂)₂(H₂O)₂]Cl₂ Single crystals of the mixed ligand complexes [Be(OSMe₂)₃(H₂O)]Cl₂ ( 2 ) and [Be(OSMe₂)₂(H₂O)₂]Cl₂ ( 3 ) were obtained from saturated solutions of [Be(OSMe₂)₄]Cl₂ ( 1 ) in acetonitrile and dichloromethane, respectively, in the presence of traces of water, while single crystals of 1 were available by reaction of the carbodiphosphorane complex [BeCl₂{C(PPh₃)₂}] with DMSO/toluene solution. All complexes are characterized by X‐ray diffraction and IR spectroscopy. 1 : Space group Pbca, Z = 8, lattice dimensions at 193 K: a = 962.4(1), b = 1888.8(2), c = 2115.8(2) pm, R₁ = 0.0344. 1 consists of [Be(OSMe₂)₄]²⁺ cations with distorted tetrahedral coordination of the oxygen atoms of the DMSO molecules with Be–O distances of 161.9 pm on average, and chloride ions. 2 : Space group , Z = 2, lattice dimensions at 193 K: a = 903.9(2), b = 925.2(3), c = 1121.3(3) pm, α = 93.65(3)°, β = 108.03(3)°, γ = 115.20(3)°, R₁ = 0.0472. 3 : Space group , Z = 2, lattice dimensions at 173 K: a = 788.2(2), b = 801.6(2), c = 1070.7(3) pm, α = 86.66(2)°, β = 83.80(2)°, γ = 71.00(2)°, R₁ = 0.0699. 2 and 3 also form dications with distorted tetrahedral coordination of the Be²⁺ ions by the oxygen atoms of DMSO and water molecules, respectively. The chloride ions are associated by strong hydrogen bonds O–H···Cl to give three‐dimensional networks.     

Die Reaktion von Molybdänpentachlorid mit (SCN)2, (SeCN)2 und ICN

Reaction of Molybdenum Pentachloride with (SCN)₂, (SeCN)₂, and ICN By reaction of MoCl₅ with (SCN)₂, (SeCN)₂, and ICN in CCl₄ or H₂CCl₂ the compounds MoCl₅(NCS)₂, MoCl₅(NCSe)₂, and MoCl₅NCI were obtained. They are very sensitive towards hydrolysis and decompose on heating. The compounds are characterized by their vibrational and EPR spectra which indicate that the pseudohalogen is bonded via a nitrogen atom.     

Synthese von Y2O2(CN2) und Leuchtstoffeigenschaften von Y2O2(CN2):Eu

Synthesis of Y₂O₂(CN₂) and Luminescence Properties of Y₂O₂(CN₂):Eu Crystalline powders of the new compound Y₂O₂(CN₂) were prepared by solid state reactions from different mixtures of YCl₃/YOCl/Y₂O₃ and Li₂(CN₂) at temperatures between 620 °C and 650 °C. Structure refinements based on X‐ray powder diffraction revealed that trigonal Y₂O₂(CN₂) crystallizes with a structure that is closely related to that of Y₂O₂S, whereas linear N‐C‐N units replace sulphur atoms in Y₂O₂S. In addition, a hexagonal polytype of Y₂O₂(CN₂) was obtained in which a different stacking sequence of yttrium atoms creates a doubling of the c‐axis. Europium‐doped samples of Y₂O₂(CN₂) were prepared and the luminescence properties of Y₂O₂(CN₂):Eu are presented.     

Diastereoselektive Synthese von β-Methyl-homoallylalkoholen durch lk-Addition von (2-Butenyl)triphenoxytitan an Aldehyde

Diastereoselective Synthesis of β-Methyl-homoallylic Alcohols by lk-Addition of (2-Butenyl)triphenoxytitanium to Aldehydes (2-Butenyl)triphenoxytitanium, prepared in situ from (2-butenyl)magnesium halogenide and chlorotriphenoxytitanium in tetrahydrofuran solution, adds to aldehydes with like (Re,Re/Si,Si?Re*,Re*) relative topicity in diastereoselectivities of 80–99%.     

Ein- und zweikernige Dinitrosylkomplexe von Molybdän und Wolfram. Die Kristallstrukturen von (PPh3Me)2[WCl4(NO)2], (PPh3Me)2[MoCl3(NO)2]2 und von (PPh3Me)2[WCl3(NO)2]2

Mono- and Binuclear Dinitrosyl Complexes of Molybdenum and Tungsten. Crystal Structures of (PPh₃Me)₂[WCl₄(NO)₂], (PPh₃Me)₂[MoCl₃(NO)₂]₂, and (PPh₃Me)₂[WCl₃(NO)₂]₂ The complexes (PPh₃Me)₂[MCl₄(NO)₂] (M = Mo, W), and (PPh₃Me)₂[MCl₃(NO)₂]₂, respectively, are prepared by reactions of the polymeric compounds MCl₂(NO)₂ with triphenylmethylphosphonium chloride in CH₂Cl₂, forming green crystals. According to the IR spectra the nitrosyl groups are in cis-position in all cases. The tungsten compounds as well as (PPh₃Me)₂[MoCl₃(NO)₂]₂ were characterized by structure determinations with X-ray methods. (PPh₃Me)₂[WCl₄(NO)₂]: space group C2/c, Z = 4. a = 1874, b = 1046, c = 2263 pm, β = 119.99°. Structure determination with 3492 independent reflexions, R = 0.057. The compound consists of PPh₃Me^⊕ ions, and anions [WCl₄(NO)₂]^2? with the nitrosyl groups in cis-position (symmetry C_2v). (PPh₃Me)₂[WCl₃(NO)₂]₂: Space group C2/c, Z = 4. Structure determination with 2947 independent reflexions, R = 0.059. (PPH₃Me)₂[MoCl₃(NO)₂]₂: Space group P1 , Z = 1. a = 989, b = 1134, c = 1186 pm; α = 63.25°, β = 80.69°, γ = 69.94°. Structure determination with 3326 independent reflexions, R = 0.046. The compounds consist of PPh₃Me^⊕ ions, and centrosymmetric anions [MCl₃(NO)₂]₂^2?, in which the metal atoms are associated via MCl₂M bridges of slightly different lengths. One of the NO groups is in an axial position, the other one in equatorial position (symmetry C_2h).     

Darstellung und Eigenschaften der Phthalocyaninato(2–)metallate(I) von Cobalt,Rhodium und Iridium; Kristallstruktur von Tetra(n-butyl)ammoniumphthalocyaninato(2–)cobaltat(I)-Aceton-Solvat

Syntheses and Properties of Phthalocyaninato(2–)metallates(I) of Cobalt, Rhodium, and Iridium; Crystal Structure of Tetra(n-butyl)ammonium Phthalocyaninato(2–)cobaltate(I) Acetone Solvate Cobaltphthalocyaninate(2–) reacts with tetra(n-butyl)ammonium boranate in acetone yielding soluble tetra(n-butyl)ammonium phthalocyaninato(2–)cobaltate(I). The green platelets of its acetone solvate crystallize in the monoclinic space group P1 2₁/c (no. 14) with cell parameters: a = 12.370(1) Å, b = 23.370(3) Å, c = 15.952(8) Å, β = 93.55(2)°, Z = 4. The Co atom is located in the centre of the distorted phthalocyaninate (waving distortion). The average Co–N_iso distance is 1.894 Å. Dichlorophthalocyaninato(2–)metal(III) acid of rhodium and iridium reacts in boiling sodium isopropylate/isopropanol with tetra(n-butyl)ammonium boranate yielding violet tetra(n-butyl)ammonium phthalocyaninato(2–)rhodate(I) and -iridate(I). The UV-VIS-NIR spectra show normal π–π* transitions of the pc^2– ligand which are shifted in the series Co < Rh < Ir to higher energy. Absorbances (in 10³ cm^–1) at 18.2/19.4/21.4/23.6 (Co), 22.0/22.8/40.4 (Rh) and 25.6 (Ir) are assigned to M → pc^2– charge transfer transitions. The vibrational spectra are typical for the pc^2– ligand. The very low absorbance of the IR bands at 916/1067/1330 cm^–1 is diagnostic for low-valent metal phthalocyaninates.