Monomere und dimere Oxovanadium(IV)-phenolate: Synthese,Struktur und Reaktionen mit reduzierenden und arylierenden Reagenzien

Monomeric and Dimeric Oxovanadium(IV)-phenolate Complexes: Synthesis, Structure, and Reaction with a Reducing and Arylation Agent Reaction of [OVCl₂(THF)₂] with LiOMes yields dimeric [Li(Et₂O)₂OVCl₂(μ-OMes)]₂ ( 1 ) which can be converted with excess LiOMes to the substitution product [Li(THF)₂OV(OMes)₃(THF)] ( 2 ). Treatment of ( 1 ) with LiMes results in the formation of complexes [Li(THF)₃OVMes₃] ( 3 ) and [Li(THF)₃OVMes₂(OMes)] ( 4 ). Complex [{Li(THF)₂OV(OMes)₂(μ-OH)}₂ · 2 THF] ( 6 ) has been isolated as a by-product of an unknown reaction of [OV(OMes)₃] and Li. The structures of 1 , 2 , 3 , and 6 have been determined by X-ray analysis. In 1 (monoclinic, P2₁/c, a = 9.522(1) Å, b = 19.777(2) Å, c = 12.311(1) Å, β = 104.45(1)°, Z = 2) the vanadium atoms which are bridged by the phenolate ligands show a square-pyramidal coordination sphere. The central atom in 2 (monoclinic, P2₁/c, a = 17.755(2) Å, b = 11.629(1) Å, c = 20.956(3) Å, β = 113.98(1)°, Z = 4) has a bipyramidal environment which is realized by coordination of a THF donor molecule. The (THF)₂Li fragment is bound via bridging phenolate ligands. The structure of 3 (orthorhombic, P2₁2₁2₁, a = 15.465(2) Å, b = 15.456(2) Å, c = 15.469(2) Å, Z = 4) is built up by two tetrahedrons linked by the oxo atom. Dimeric 6 (triclinic, P1, a = 10.780(4) Å, b = 11.428(2) Å, c = 13.734(3) Å, α = 77.24(2)°, β = 84.79(2)°, γ = 74.35(2)°, Z = 1) has a structure similar to 1 . The vanadium atoms are bridged by two OH groups while phenolate ligands link the lithium cations with the vanadium atoms.     

Syntheses and X‐Ray Crystal Structures of New Copper(I) and Silver(I) Complexes containing Thione Ligands

The reaction of [(Ph₃P)₂CuCl]₂ with 4‐amino‐6‐methyl‐1,2,4‐triazine‐thione‐5‐one (AMTTO, 1 ) in methanol and further recrystallization from methanol/acetone solution gives [(C₄H₄N₃SON(=CMe₂)Cu(PPh₃)₂Cl] ( 2 ) as a neutral complex. [(C₄H₄N₃SON(=CMe₂)Ag(PPh₃)₂]NO₃ ( 4 ) can be obtained in excellent yield by the reaction of [(AMTTO)₂Ag]NO₃ ( 3 ) with triphenylphosphane in methanol/acetone. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at –80 °C: space group P1 with a = 1233.8(1), b = 1389.7(1), c = 1417.1(1) pm, α = 89.36(1)°; β = 65.10(1)°, γ = 65.95(1)°, Z = 2, R₁ = 0.0582 and for 4 at –80 °C: space group P1, with a = 1193.3(1), b = 1308.5(1), c = 1385.3(1) pm, α = 94.69(1)°, β = 109.14(1)°, γ = 93.42(1)°, Z = 2, R₁ = 0.0716.     

[ScCl2{N(SiMe3)2}(THF)2] als Vorläufer für die Synthese von Scandiumnitrid

[ScCl₂{N(SiMe₃)₂}(THF)₂] – a Precursor for the Synthesis of Scandium Nitride [ScCl₂{N(SiMe₃)₂}(THF)₂] ( 1 ) has been prepared by the reaction of [ScCl₃(THF)₃] with the trisamide Sc[N(SiMe₃)₂]₃ in tetrahydrofurane solution forming colourless moisture sensitive crystals, which were characterized by a crystal structure determination. Space group P 1, Z = 2, lattice dimensions at –50 °C: a = 841.4(1), b = 924.2(1), c = 1550.0(1) pm, α = 90.046(7)°, β = 95.671(9)°, γ = 106.066(6)°, R₁ = 0.0329. In the molecular structure of 1 the scandium atom has a distorted trigonal‐bipyramidal coordination with the THF molecules in apical positions. At 400 °C 1 is converted into scandium nitride, ScN, by stepwise leaving of THF and ClSiMe₃.     

Triphenylphosphinimino‐triphenylstiboniumchlorid, [Ph3PNSbPh3Cl], und seine Reaktion mit FeCl3

[Ph₃PNSbPh₃Cl] ( 1 ) was prepared by oxidative addition of ClNPPh₃ to triphenylstibine in dichloromethane solution. The compound is characterized by IR spectroscopy and by an X‐ray structure determination. 1 crystallizes in the monoclinic space group P2₁/c with four formula units per unit cell. Lattice dimensions at 193 K: a = 925.3(1), b = 1777.2(1), c = 1825.5(1) pm, β = 94.07(1)°, R₁ = 0.0228. 1 forms monomeric molecules with tetrahedrally coordinated phosphorus and trigonal‐bipyramidally coordinated antimony atom, the atoms N and Cl being in axial positions. The bond lengths PN and SbN are 155.0(2) and 198.4(2) pm, respectively, the PNSb angle is 138.6(1)°. 1 reacts with iron trichloride to give the known phosphoraneiminato complex [FeCl₂(NPPh₃)]₂.     

Copper(II) chloride complex with bis-1,1′-(3,3-dimethyl-3,4-dihydroisoquinoline): Crystal structure

The copper chloride complex with bis-1,1′-(3,3-dimethyl-3,4-dihydroisoquinoline) (L) was synthesized and characterized by X-ray diffraction and UV/Vis and IR spectroscopy. The structure of the complex [Cu₂L₂Cl₄] is built of centrosymmetric binuclear molecules with a double chlorine bridge. The coordination five-vertex polyhedron of copper is a heavily distorted tetragonal pyramid with a considerably nonplanar base in which the vertices are occupied by chlorine atoms (bridging Cl(1) and Cl(1A) and terminal Cl(2)) and the nitrogen atom N(2); the axial vertex is occupied by N(1). The bond lengths, Cu-N_eq (2.013(1) Å), Cu-N_ax (2.392(2) Å), Cu-Cl_bridge (2.305(1) and 2.342(1)), and Cu-N_term (2.251(1) Å), are markedly different. The coordinated ligand occurs in the cisoid form (the N(1)C(1)C(12)N(2) torsion angle is ?32.6°).     

Diacyltelluride: Synthesen durch Reaktionen von Acylchloriden mit Bis(trialkylsilyl)telluriden; Strukturbestimmungen an Di(1-adamantoyl)tellurid und Adamantancarbonsäureanhydrid

Diacyltellurides: Synthesis by Reactions of Acyl Chlorides with Bis(trialkylsilyl)tellurides. Structure Determinations of Di(1-adamantoyl)telluride and Adamantanecarbonic Anhydride Bis(isopropyldimethylsilyl)telluride ( 1 ) is prepared from tellurium with lithiumtriethylhydridoborate and chloro(isopropyl)dimethylsilane. From reactions of acylchlorides RCOCl with 1 , diacyltellurides (RCO)₂Te (R = CH₃- 2 , i-C₃H₇- 3 , i-C₄H₉- 4 , (CH₃)₃CH₂-) 5 are isolated in pure state after removal of chloro(isopropyl)dimethylsilane. With succinic and glutaric dichlorides, 1 leads to impure cyclic diacyltellurides 6 (tellurosuccinic anhydride) and 7 (telluroglutaric anhydride). The reactions of bulky pivaloyl chloride and 1-adamantoyl chloride with 1 are too slow to be synthetically useful, but using bis(trimethylsilyl)telluride, dipivaloyltelluride 8 and di(1-adamantoyl)telluride 9 are straightforwardly available. 9 is accompanied by traces of 1-adamantanecarbonic anhydride 10 and by small amounts of di(1-adamantyl)ditelluride 11 . Constitutions of the new compounds 1 , 3–7 and 9 were confirmed by multinuclear NMR and mass spectroscopy. The structures of 9 and 10 were determined by X-ray crystallography.     

Phosphaniminate von Alkalimetallen: Die Kristallstrukturen von [KNPCy3]4, [KNPCy3]4·2OPCy3, [CsNPCy3]4·4OPCy3 und [Li4(NPPh3)(OSiMe2NPPh3)3(DME)]

The alkalimetal phosphoraneiminates [KNPCy₃]₄, ( 1 ) [KNPCy₃]₄·2OPCy₃ ( 2 ) and [CsNPCy₃]₄·4OPCy₃ ( 3 ) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy₃PI₂ or Cy₃PBr₂ in liquid ammonia, as well as the lithium derivative [Li₄(NPPh₃)(OSiMe₂NPPh₃)₃(DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe₂)n into the LiN bonds of [LiNPPh₃]₆ in DME solution (DME = 1, 2‐dimethoxyethane). 1 : Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2 : Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3 : Space group Cmc2₁, Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4 ·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ₃‐NPCy₃^‐) groups, whereas 4 forms a "heteroleptic" Li₄NO₃ heterocubane.     

Synthese und Kristallstruktur des Azidoberyllats (Ph4P)2[Be(μ‐OSiMe3)(N3)2]2

Synthesis and Crystal Structure of the Azido Beryllate (Ph₄P)₂[Be(μ‐OSiMe₃)(N₃)₂]₂ (Ph₄P)₂[Be₂F₆] reacts with excess trimethylsilylazide in acetonitrile solution, accompanied by a hydrolytic side‐reaction to give the azido beryllate (Ph₄P)₂[Be(μ‐OSiMe₃)(N₃)₂]₂ ( 1 ) as colourless, non‐explosive crystals. 1 was characterized by IR spectroscopy and by single crystal X‐ray determination. 1 : Space group , Z = 1, lattice dimensions at 193 K: a = 1026.9(1), b = 1184.0(1), c = 1352.1(1) pm, α = 73.50(1)°, β = 74.35(1)°, γ = 64.66(1)°, R₁ = 0.0543. The complex anion of 1 forms centrosymmetric units with symmetry C_i via Be₂O₂ four‐membered rings with Be–O distances of 159.2(7) and 168.7(7) pm, and terminally bonded azide groups.     

Phase Width and Site Preferences in the EuMgxGa4−x Series

A series of EuMg_xGa_4?x compounds were synthesized using high temperature, solid‐state methods and characterized by both powder and single crystal X‐ray diffraction. All compounds crystallize in the tetragonal BaAl₄‐type structure (space group I4/mmm, Z = 2, Pearson symbol tI10) with full occupancy of Ga at the apical atom (4e) site and mixed‐occupancy of Mg and Ga at the basal atom (4d) site. Six compositions were analyzed by single crystal X‐ray diffraction: EuMg_0.21(1)Ga_3.79(1), EuMg_0.91(1)Ga_3.09(1), EuMg_1.22(1)Ga_2.78(1), EuMg_1.78(1)Ga_2.22(1), EuMg_1.84(1)Ga_2.16(1), and EuMg_1.94(1)Ga_2.06(1). As the larger Mg atoms increasingly replace Ga atoms at the basal site in EuMg_xGa_4?x, the a‐axis lengths at first decrease and then increase, while the c‐axis lengths increase monotonically along the series. The phase width of the BaAl₄‐type EuMg_xGa_4?x series is identified to be 0 ≤ x ≤ 1.94(1), a range which corresponds to 12.06(1)‐14 valence electrons per formula unit, and can be understood by their electronic structures using density of states (DOS) curves calculated by tight‐binding calculations. Mg substitution for Ga at the basal site is consistent with the site preferences for mixed metals on the three‐dimensional framework of the BaAl₄‐structure based on both electronegativities and sizes, and provides the rationale for the unusual behavior in lattice parameters. The observed site preference was also rationalized by total electronic energies calculated for two different coloring schemes.     

Supramolecular and metallosupramolecular coordination compounds of nickel(II) with the half units of vicinal oxime–imine ligands; mixed ligand complexes of the metal ion

The [1+1] condensation of isonitrosoacetylacetone (Hisoacac) with o-phenylenediamine produces the diazepine (HLBD) (1), which reacts with Ni(OAc)₂· 4H₂O (1:1 molar ratio) to produce the mixed ligand complex (LBDN)Ni(OAc) (2); where LBDN is the anion of the half unit obtained by hydrolysis of one HLBD imine linkage. The reaction of (2) (1 mol) with mono-, bi- and trichloroethanoic acid (1mol) or picric acid (1mol) led to the exchange of the acetate in (2) with the anion of the added acid [(3)–(6), respectively]. The supramolecular structure of (2)–(6) is achieved through the dimerization of these complexes via intermolecular hydrogen bonding of the LBDN –NH₂ group of one molecule and the monodentate acetate group of another molecule. The template reaction of o-phen with Hisoacac in the presence of Ni(OAc)₂·4H₂O (1:2:2 and 1:2:1 molar ratios, respectively) led to the formation of (LBDN)Ni(OAc)₂Ni(isoacac) (7) and (isophen)Ni (8), respectively; H₂isophen is a symmetrical Schiff base ligand formed by the (2:1) in situ condensation of Hisoacac with o-phen. The (1:1) condensation of Hisoacac with p-phen produced the half unit Hisopphen (9), whose 1:1 molar ratio reaction with Ni(OAc)₂·4H₂O led to the formation of (isopphen)Ni(OAc)·2H₂O (10). The amino group of the isopphen ligand is available for further coordination with the nickel(II) ion to produce the metallosupramolecular complexes {[two molecules of complex (10)] [Ni(OAc)₂]} and {[complex (10)] [Ni(OAc)₂·H₂O]} from the 2:1 and 1:1 molar ratio reactions, respectively, of (10) with Ni(OAc)₂·4H2O. The 1:1 molar ratio reaction of (10) with Hisoacac led to replacement of OAc by isoacac. The suggested structures of the ligands and their coordination compounds are based on analytical, chemical, spectral data and magnetic moments.     

{(MesGa)3[GaP(H)Mes](PMes)4}, Ein phosphorsubstituiertes Ga?P-Heterocuban

{(MesGa)₃[GaP(H)Mes](PMes)₄}, a Phosphorus-substituted Ga? P-Heterocubane A mixture of MesGaCl₂/GaCl₃ (ratio 3:1) reacts with 5 equivalents of MesPLi₂ in THF at ?78°C to the title compound {(MesGa)₃[GaP(H)Mes](PMes)₄} ( 1 ) by use of the “dilution principle”. 1 can be obtained in 30% yield. Recrystallization of 1 from DME and toluene, respectively, gives 1 · 0.5 DME and 1 · toluene. 1 was characterized by NMR-, IR-, and MS-techniques. According to the X-ray structure determination of 1 · toluene, 1 has a heterocubane structure, one corner of which is substituted with an P(H)Mes group.     

Diacetonalkohol‐Komplexe von Lanthanoid‐Trichloriden. Die Kristallstrukturen von [LnCl3(DAA)2] mit Ln = Sm und Eu

Diacetone Alcohol Complexes of Lanthanide Trichlorides. Crystal Structures of [LnCl₃(DAA)₂] with Ln = Sm and Eu The diacetone alcohol complexes [LnCl₃(DAA)₂] with Ln = samarium ( 1 ) and europium ( 2 ) are obtained from the waterfree metal trichlorides with excess diacetone alcohol (4‐hydroxy‐4‐methyl‐2‐pentanone = DAA) forming colourless ( 1 ) and pale yellow crystals ( 2 ), respectively, which are characterized by crystal structure determinations. The europium compound 2 is additionally described by its vibrational spectra (IR, Raman). 1 and 2 crystallize isotypically with one another. The metal atoms of the molecular complex units are unusually coordinated in a distorted pentagonal‐bipyramdial fashion by the three chlorine atoms and by the two alcoholic oxygen atoms of the DAA molecules in the equatorial plane. The apical positions are occupied by the carbonyl oxygen atoms of the chelating DAA molecules. The complex units [LnCl₃(DAA)₂] are associated along [100] by bifurcated —OH···Cl···HO— bridges to form chains. 1 : Space group P2₁, Z = 2, lattice dimensions at —80 °C: : a = 710.2(1), b = 1617.6(2), c = 827.3(1) pm; β = 106.36(1)°; R₁ = 0.026. 2 : Space group P2₁, Z = 2, lattice dimensions at —80 °C: a = 709.7(1), b = 1614.5(2), c = 825.7(1) pm; β = 106.40(1)°; R₁ = 0.0303.     

Syntheses and Molecular Structures of Titanium Derivatives with Polymerizable Ligands. Toward Extended Arrays

The reactions between Ti(OR)₄ and allylacetatoacetate (HAAA) in 1:1 or 1:2 stoichiometry at rt gave Ti₂(OR)₆(AAA)₂ R = Et ( 1 ), iPr ( 2 ) and Ti(OR)₂(AAA)₂ R = Et ( 3 ), iPr ( 4 ) species. A monosubstituted derivative Ti₂(OiPr)₆(AMP)₂ ( 5 ) was isolated with allylmethylphenol (AMPH). 1 and 5 were characterized by single crystal X‐ray diffraction. Their molecular structures consist of dimers with the polymerizable ligands in terminal positions andbridging alkoxide ligands assembling five and six‐coordinated metal atoms, respectively. The Ti‐O bond lengths of 1 are in the range 1.76(1) to 2.11(1) Å with the variation Ti‐OEt < Ti‐μ‐OEt < Ti‐η²‐O (allylacetatoacetate). All compounds were characterized by FT‐IR and ¹H NMR. The possibility to accede to more extended arrays either by hydrolysis or by radical initiated homo‐ or co‐polymerization reactions was investigated for the allylacetato derivatives as well as for Ti(OiPr)₂(AAEMA)₂ AAEMA = [2‐(methacryloyloxy)ethylacetoacetato] for the latter reactions.     

New examples of mixed-ligand bis(hexafluoroacetylacenonato)copper(II) complexes with 3-imidazoline nitroxide radicals at a Cu(C5HF6O2)2∶L=3∶2 ratio (L2=C14H19N2O,L3=C13H17N2O3)

The crystal structures of two (hexafluoroacetylacetonato)copper(II) complexes with 3-imidazoline nitroxide radicals, [Cu(C₅HF₆O₂)₂]₃ (C₁₄H₁₉N₂O)₂ (I) and [Cu(C₅HF₆O₂)₂]₃ (C₁₃H₁₇N₂O₃)₂ (II), have been determined. The compounds are triclinic (PI, Z=1) with a=8.730(2), b=10.357(2), c=21.996(5) Å, α=103.24(2), β=94.03(2), γ=95.04(2)⁰, V=1920(1) ų for I and a=8.679(2), b=14.769(4), c=15.368(4) Å, α=85.58(2), β=96.25(1), γ=104.60(1)⁰, V=1893(1) ų for II. Complexes I and II are molecular. The trinuclear molecules are centrosymmetric relative to the Cu(1) atom. The coordination polyhedron of Cu(1) is a square bipyramid formed by the O atoms of the hfac anions and nitroxide radicals (average Cu?O_hfac 1.92(1) for I and 1.93(1) Å for II; Cu?O_N?O 2.47(1) for I and 2.56(1) Å for II). The coordination polyhedron of Cu(2) is a trigonal bipyramid formed by the O atoms of the hfac anions (Cu?O_hfac 1.91(1)–2.12(1) for I and 1.91(1)–2.09(1) Å for II) and an imine N atom of the radical (Cu(2)?N(2) 2.00(1) for I and 2.03(1) Å for II). The molecules are linked by van der Waals forces.     

Synthese,Schwingungsspektrum und Kristallstruktur des Disiloxanato‐Chloroberyllats (Ph4P)2[Be4Cl6(OSiMe2OSiMe2O)2]

Synthesis, Vibrational Spectra, and Crystal Structure of the Disiloxanato‐chloroberyllate (Ph₄P)₂[Be₄Cl₆(OSiMe₂OSiMe₂O)₂] (Ph₄P)₂[Be₄Cl₆(OSiMe₂OSiMe₂O)₂] ( 1 ) was prepared by the reaction of (Ph₄P)₂[Be₂Cl₆] with cyclo‐hexamethyl‐trisiloxane in dichloromethane solution, forming colourless, moisture sensitive crystals, which are characterized by their vibrational spectra (IR, Raman) and by an X‐ray crystal structure determination. 1 crystallizes in the triclinic space group with Z = 1 and with the lattice dimensions at 193 K: a = 1050.0(1), b = 1248.2(1), c = 1312.5(1) pm, α = 84.37(1)°; β = 76.53(1)°; γ = 70.79(1)°; R₁ = 0.0349. 1 consists of (Ph₄P)⁺ions and centrosymmetric anions [Be₄Cl₆(OSiMe₂OSiMe₂O)₂]^2‐, in which the four beryllium atoms are connected by the terminal oxygen atoms of the (OSiMe₂OSiMe₂O)^2‐ ligands via two‐forked bonds to give Be₂O₂ four‐membered rings. The Be atoms of these units are additionally bridged by two μ‐Cl atoms. 1 is also obtained by reaction of (Ph₄P)₂[Be₂Cl₆] with Baysilon grease.     

Compounds of palladium halides with substituted imidazoles

Summary Compounds of the type PdL₂X₂ (L=1-methylimidazole, 1-vinylimidazole, 1-n-butylimidazole, 1,2-dimethylimidazole, 1-vinyl-2-methylimidazole, 1,2-dimethyl-5-nitroimidazole, 2-isopropyl-4(5)-nitroimidazole and 2-methyl-4(5)-nitro-imidazole; X=Cl or Br) are obtained by treating PdX₂ (1 mole) with solutions of the ligands L (2 moles). An excess of L gives PdL₄X₂ complexes (L=1-methylimidazole, 1-vinylimidazole, 1,2-dimethylimidazole and 1-vinyl-2-methylimidazole). The compounds were characterized by chemical analyses, molar conductivity measurements and i.r. spectra.     

Controlled polymerization of an AB2 monomer using a chloromethylarene as comonomer: branched polymers from activated methylene compounds

Hyperbranched and branched polymers were synthesized by one-pot reaction of the AB₂ monomer 4-(4′-chloromethylbenzyloxy)phenylacetonitrile (1 ). The polymerization of 1 was controlled by adding a chloromethylarene (A₁ comonomer) such as methoxybenzyl chloride and by adding TBAC (tetrabutylammonium chloride). Copolymerization of 1 with A₂ comonomers, bis(chloromethyl)arenes, gives the corresponding copolymers.     

Über die Reaktionen sterisch aufwendig substituierter Phosphine am Beispiel des 1-Adamantylphosphins

The Reactions of Primary Phosphines Involving Sterically Demanding Substituents: The Case of 1-Adamantylphosphine The reaction of 1-AdPH₂ 1 with equimolar amounts of H₂O₂ · C(:O)(NH₂)₂, sulfur and selenium furnished the corresponding primary phosphine oxides, sulfides and selenides, 2, 5 and 7 . In these compounds the PH-protons may be exchanged quantitatively for deuterons by the action of CH₃OD/trifluoroacetic acid anhydride, while the reaction of 1 with the same agent gave a mixture of 1-AdPH₂ 1 , 1-AdPHD 1a and 1-AdPD₂ 1b . The reaction of 1 with activated carbonyl compounds, R¹R²C(:O) led to the di-adducts 9 and 10 and to the mono-adduct 11 of the general type 1-AdPH_2–n[C(OH)R¹R²]_n [n = 2 for 9 (R¹ = H, R² = CCl₃) and 10 (R¹ = H, R² = COOH); n = 1 for 11 (R¹ = Ph, R² = CF₃)]. 11 decomposed in solution, giving 1-AdPH₂ 1 and trifluoroacetophenone. 1-Adamantylphospholanium tribromide 12 was synthesized by heating 1 in 1,4-dibromobutane and was converted into the corresponding hexafluorophosphate 12a and the oxide 13 . The action of a 2.5-fold excess of phosgene on 1 gave 1-AdPCl₂ 15 in high yield. The reaction of 1-AdPH₂ 1 with Ph₃SnCl led to the formation of P? Sn-bonds. An attempt at the separation of the mixture of the mono- and distannylation products, 16 and 17 , was unsuccessful. Metal complexes of the type cis-(1-AdPH₂)₂MCl₂ (M = Pd: 18 , M = Pt: 19 ) were obtained by reaction of 1-AdPH₂ 1 with (COD)MCl₂ (COD = 1,5-cyclo-octadiene). In the same way (NOR)Mo(CO)₄ (NOR = norbornadiene) and (CHT)Mo(CO)₃ (CHT = cycloheptatriene) reacted with two or three equivalents of 1 to give the expected co-ordination compounds, cis-L₂Mo(CO)₄ 21 and fac-L₃Mo(CO)₃ 22 (L = 1 ), respectively. The phosphido complex Cp(CO)₂Mo(μ-1-AdPH)(μ-H)Mo(CO)₂Cp 23 (Cp = cyclopentadienyl) was formed by refluxing a solution of 1 and [CpMo(CO)₃]₂ in methylcyclohexane.     

Synthesis,Characterization and Crystal Structures of new Palladium(II) Complexes and the first Platinum(III) Complex Containing ATT (ATT = 6‐Aza‐2‐thiothymine)

Treatment of the ligand 6‐aza‐2‐thiothymine (ATT, HL, 1 ) with palladium chloride in methanol forms the ionic complex [(HL)₄Pd]Cl₂·8MeOH ( 2 ), while its reaction with palladium iodide in same solvent produces the neutral complex trans‐[(HL)₂PdI₂]·2MeOH ( 3 ) in high yields. The reaction of 1 with Na₂[PdCl₄] in the presence of sodium acetate in a molar ratio of 2:1:2 and with platinum(II) chloride in presence of sodium acetate led to the dimer tetranuclear complexes [(L₄Pd₂)NaCl]₂·8MeOH ( 4 ) and [L₄Pt₂Cl₂]·6MeOH·H₂O ( 5 ). The latter is the first Pt^III complex of the ligand. All complexes were characterized by elemental analyses and IR spectroscopy and the crystal structures of 2 , 3 , 4 and 5 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: triclinic space group , a = 1006.6(1), b = 1006.9(1), c = 1158.1(1) pm, α = 85.20(1)°, β = 83.84(1)°, γ = 88.91(1)°, Z = 1, R₁ = 0.0278; for 3 at ?80 °C: triclinic space group , a = 490.5(1), b = 977.2(2), c = 1116.8(2) pm, α = 90.26(1)°, β = 102.33(1)°, γ = 96.08(1)°, Z = 1, R₁ = 0.0394; for 4 at ?80 °C: orthorhombic space group Ccca, a = 1791.7(2), b = 1874.1(2), c = 2044.0(1) pm, Z = 4, R₁ = 0.0341 and for 5 at ?80 °C: monoclinic space group P2₁/c, a = 1464.3(1), b = 2003.7(1), c = 1368.5(1) pm, β = 95.66(1)°, Z = 4, R₁ = 0.0429.     

Spektroskopische Charakterisierung und Kristallstruktur von Trifluormethylchloriod(III)‐trifluoracetat (CF3I(Cl)OCOCF3)

Spectroscopic Characterization and Crystal Structure of Trifluoromethyl Iodine(III) Chloride Trifluororacetate (CF₃I(Cl)OCOCF₃) The ternary iodine(III) compound CF₃I(Cl)OCOCF₃ is obtained by reaction between CF₃I(Cl)F and (CH₃)₃SiOCOCF₃ at –50 °C. The molecule was characterized by vibrational spectra, NMR‐spectra, and a crystal structure analysis. CF₃I(Cl)OCOCF₃ crystallizes monoclinic in the space group P2₁/c with a = 1102.7(1) pm, b = 785.6(1) pm, c = 989.7(1) pm, and β = 101.34(1)°.