Piperazine Functionalization of C70 for Incorporation into Supramolecular Assemblies

The photochemical reaction of piperazine with C₇₀ produces a mono‐adduct (N(CH₂CH₂)₂NC₇₀) in high yield (67 %) along with three bis‐adducts. These piperazine adducts can combine with various Lewis acids to form crystalline supramolecular aggregates suitable for X‐ray diffraction. The structure of the mono‐adduct was determined from examination of the adduct I₂N(CH₂CH₂)₂NI₂C₇₀ that was formed by reaction of N(CH₂CH₂)₂NC₇₀ with I₂. Crystals of polymeric {Rh₂(O₂CCF₃)₄N(CH₂CH₂)₂NC₇₀}_n?nC₆H₆ that formed from reaction of the mono‐adduct with Rh₂(O₂CCF₃)₄ contain a sinusoidal strand of alternating molecules of N(CH₂CH₂)₂NC₇₀ and Rh₂(O₂CCF₃)₄ connected through Rh?N bonds. Silver nitrate reacts with N(CH₂CH₂)₂NC₇₀ to form black crystals of {(Ag(NO₃))₄(N(CH₂CH₂)₂NC₇₀)₄}_n?7nCH₂Cl₂ that contain parallel, nearly linear chains of alternating (N(CH₂CH₂)₂NC₇₀ molecules and silver ions. Four of these {Ag(NO₃)N(CH₂CH₂)₂NC₇₀}_n chains adopt a structure that resembles a columnar micelle with the ionic silver nitrate portion in the center and the nearly non‐polar C₇₀ cages encircling that core. Of the three bis‐adducts, one was definitively identified through crystallization in the presence of I₂ as ¹²{N(CH₂CH₂)₂N}₂C₇₀ with addends on opposite poles of the C₇₀ cage and a structure with C_2v symmetry. In ¹²{I₂N(CH₂CH₂)₂N}₂C₇₀, individual ¹²{I₂N(CH₂CH₂)₂N}₂C₇₀ units are further connected by secondary I2???N2 interactions to form chains that occur in layers within the crystal. Halogen bond formation between a Lewis base such as a tertiary amine and I₂ is suggested as a method to produce ordered crystals with complex supramolecular structures from substances that are otherwise difficult to crystallize.     

π-Olefin-iridium-komplexe : IV. Umsetzungen von chloro-dien-iridium-verbindungen mit lithiumorganylen

The complexes [(1,3-C₆H₈)₂IrR] and [(1,3-C₇H₁₀)₂IrR] (R = CH₃, C₆H₅) are obtained by reaction of the corresponding chloro compounds with RLi. Interaction of [Ir(COD)Cl]₂ (COD = 1,5-cyclooctadiene) with CH₃Li in the presence of 1,3-cyclohexadiene or isoprene yields [(COD)(1,3-C₆H₈IrCH₃] and [(COD)(C₅H₈IrCH₃], respectively. The products of the reaction of chlorodicyclodieneiridium with n-C₄H₉Li depend on the ring size of the cyclodiene ligands; with 1,3-cyclohexadiene [(1,3-C₆H₈)₂IrH] is formed while with 1,3-cycloheptadiene [(1,3-C₇H₁₀)(C₇H₉)Ir] is obtained together with [(1,3-C₇H₁₀)₃Ir₂(μ-H)₂]. Chemical and spectroscopic properties of the new compounds are discussed.     

The synthesis and structure of triphenylsiloxycyclotriphosphazenes

The triphenylsiloxy-substituted cyclotriphosphazenes, N₃P₃Cl₅OSiPh₃, gem-N₃P₃Cl₄(OSiPh₃)₂, N₃P₃(OSiPh₃)₆, and N₃P₃(OPh)₅OSiPh₃, have been prepared. The synthesis of gem-N₃P₃Cl₄(OSiPh₃)₂ involves the reaction of (NPCl₂)₃ with Ph₃SiONa to form the intermediates gem-N₃P₃Cl₄(OSiPh₃)₂(ONa) and gem-N₃P₃Cl₄(ONa)₂, which yield gem-N₃P₃Cl₄(OSiPh₃)₂ when treated with Ph₃SiCl. The compounds N₃P₃Cl₅OSiPh₃ and N₃P₃(OSiPh₃)₀ are formed by the condensation reactions of N₃P₃Cl₅OBuⁿ and N₃P₃(OBuⁿ)₆, respectively, with Ph₃SiCl. The compound N₃P₃(OPh)₅OSiPh₃ is synthesized by the reaction between N₃P₃(OPh)₅Cl and Et₃SiONa to first give the intermediate N₃P₃(OPh)₅ONa, which yields N₃P₃(OPh)₅OSiPh₃ when reacted with Ph₃SiCl. The structural characterization and properties of these compounds are discussed. The crystal and molecular structure of gem-N₃P₃Cl₄(OSiPh₃)₂ has been investigated by single-crystal X-ray diffraction techniques. The crystals are monoclinic with the space group P2₁/c with a = 16.850(8), b = 12.829(4), c = 18.505(15) Å, and β = 101.00(6)° with V = 3927 ų and Z = 4. © 1996 John Wiley & Sons, Inc.     

Bildung siliciumorganischer Verbindungen. 73. Reaktionen C-chlorierter 1,3-Disilapropane mit CH3MgCl

Formation of Organosilicon Compounds. 73. Reactions of C-chlorinated 1,3-Disilapropanes with CH₃MgCl (Cl₃Si)₂CCl₂ reacts with an excess of meMgCl (me = CH₃) in Et₂O (diethylether) forming (me₃Si)₂₂C?CH₂ mainly besides Si-methylated 1,3-disilapropanes with CmeCl, CHCl, CH₂ groups [6]. For investigating the mechanism of formation of the methylidengroup reactions were carried out with differently Si-methylated and Si-chlorinated 2-methyl-1-2-chloro-1,3-disilapropanes and 2,2-dichloro-1,3-disilapropanes. Whereas (me₃Si)₂CmeCl reacts neither with meMgCl nor with Lime. it forms (me₃Si)₂C?CH₂ and (me₃Si)₂CmeH with Li or Mg resp. The reaction starts with the metallation to (me₃Si)₂CmeLi and (me₃Si)₂Cme(MgCl) resp., followed by elimination of LiH and HMgCl resp. with formation of (me₃Si)₂C?CH₂. LiH and HMgCl resp. reduces (me₃Si)₂CmeCl to (me₃Si)₂CmeH. This mechanism is supported by the reactions of (me₃Si)₂CCl(CD₃). The Si-chlorination increases the reactivity of the CmeCl group and the created C?CH₂ group favours Si-methylation. The CCl₂ group is more reactive than the CmeCl group; (me₃Si)₂CCl₂ already forms the methyliden group with meMgCl in Et₂O via the not isolated intermediate (me₃Si)₂CCl(MgCl). which prefers the methylation to (me₃Si)₂Cme(MgCl). The n.m.r. data of the investigated compounds are given.     

Molten salt synthesis of potassium and barium niobates

The interaction of powdered niobium oxide with molten potassium and barium nitrate salts containing KOH was studied. It was shown that KNbO₃ can be obtained with the use of binary mixtures of the KOH-KNO₃ system. The BaNb₂O₆ compound can be synthesized in melts of the KNO₃-Ba(NO₃)₂ system. The treatment of Nb₂O₅ with melts of the system KNO₃-Ba(NO₃)₂-KOH with various KOH percentages allowed us to obtain mixtures of Ba₅Nb₄O_15.33 with Nb₁₂O₂₉ or Ba₅Nb₄O_15.48 with K_0.8Ba_0.2NbO₃.     

Synthesis of Inorganic Structural Isomers By Diffusion‐Constrained Self‐Assembly of Designed Precursors: A Novel Type of Isomerism

The structure of precursors is used to control the formation of six possible structural isomers that contain four structural units of PbSe and four structural units of NbSe₂: [(PbSe)_1.14]₄[NbSe₂]₄, [(PbSe)_1.14]₃[NbSe₂]₃[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₃[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₂, [(PbSe)_1.14]₂[NbSe₂]₃[(PbSe)_1.14]₂[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₁, [(PbSe)_1.14]₂[NbSe₂]₁[(PbSe)_1.14]₁[NbSe₂]₂[(PbSe)_1.14]₁[NbSe₂]₁. The electrical properties of these compounds vary with the nanoarchitecture. For each pair of constituents, over 20 000 new compounds, each with a specific nanoarchitecture, are possible with the number of structural units equal to 10 or less. This provides opportunities to systematically correlate structure with properties and hence optimize performance.     

Spinel, YbFe2O4, and Yb2Fe3O7 types of structures for compounds in the In2O3 and Sc2O3---A2O3---BO systems [A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, Cu, or Zn] at temperatures over 1000°C

In the Sc₂O₃---Ga₂O₃---CuO, Sc₂O₃---Ga₂O₃---ZnO, and Sc₂O₃---Al₂O₃---CuO systems, ScGaCuO₄, ScGaZnO₄, and ScAlCuO₄ with the YbFe₂O₄-type structure and Sc₂Ga₂CuO₇ with the Yb₂Fe₃O₇-type structure were obtained. In the In₂O₃---A₂O₃---BO systems (A: Fe, Ga, or Al; B: Mg, Mn, Fe, Ni, or Zn), InGaFeO₄, InGaNiO₄, and InFe³⁺MgO₄ with the spinel structure, InGaZnO₄, InGaMgO₄, and InAlCuO₄ with the YbFe₂O₄-type structure, and In₂Ga₂MnO₇ and In₂Ga₂ZnO₇ with the Yb₂Fe₃O₇-type structure were obtained. InGaMnO₄ and InFe₂O₄ had both the YbFe₂O₄-type and spinel-type structures. The revised classification for the crystal structures of AB₂O₄ compounds is presented, based upon the coordination numbers of constituent A and B cations.     

Low oxidation state ruthenium chemistry : IV. The reactions of M(CO)2(PPh3)3 complexes (M = Fe,Ru) and the hydrogenation and isomerization of alkenes catalyzed by RuL(CO)2(PPh3)2 (L = H2, PPh3)

The complexes M(CO)₂(PPh₃)₃ (I, M = Fe; II, M = Ru) readily react with H₂ at room temperature and atmospheric pressure to give cis-M(H)₂(CO)₂(PPh₃)₂ (III, M = Fe;IV,M = Ru). I reacts with O₂ to give an unstable compound in solution, in a type of reaction known to occur with II which leads to cis-Ru(O₂)(CO)₂(PPh₃)₂(V). Even compound IV reacts with O₂ to give V with displacement of H₂; this reaction has been shown to be reversible and this is the first case where the displacement of H₂ by O₂ and that of O₂ by H₂ at a metal center has been observed. III and IV are reduced to M(CO)₃(PPh₃)₂ by CO with displacement of H₂; Ru(CO)₃- (PPh₃)₂ is also formed by treatment of IV with CO₂, but under higher pressure. Compounds II and IV react with CH₂CHCN to give Ru(CH₂CHCN)(CO)₂- (PPh₃)₂(VI) which reacts with H₂ to reform the hydride IV.cis-Ru(H)₂(CO)₂(PPh₃)₂(IV) has been studied as catalyst in the hydrogenation and isomerization of a series of monoenes and dienes. The catalysts are poisoned by the presence of free triphenylphosphine. On the other hand the ready exchange of H₂ and O₂ on the “Ru(CO)₂(PPh₃)₂” moiety makes IV a catalyst not irreversibly poisoned by the presence of air. It has been found that even Ru(CO)₂(PPh₃)₃(II) acts as a catalyst for the isomerization of hex-1-ene at room temperature under an inert atmosphere.     

Perfluoralkyljod-verbindungen: das trifluormethyljoddinitrat CF3J(NO3)2

CF₃I(NO₃)₂ is formed from the reactions of CF₃IF₂ or CF₃IO with N₂O₅ as well as CF₃I with ClNO₃. During the reactions of CF₃IF₂ with N₂O₅ or CF₃I with ClNO₃ the intermediate products CF₃IF(NO₃) or CF₃ICl(NO₃) can be identified. The preparations, properties, ¹⁹F-nmr spectra and the thermal decomposition of CF₃I(NO₃)₂ are described.     

Antimon-organo-Verbindungen. V. Zum Reaktionsverhalten des Phenylstibins

Organoantimony Compounds. V. The Reactivity of Phenyl Stibine C₆H₅SbH₂, synthesized by the reduction of C₆H₅SbCl₂ with LiBH₄, reacts with LiR under certain conditions forming (C₆H₅Sb)_n and H₂ or give by a partially elimination of H₂ stibides with a different structure. The latter react with alkyl and aryl halides forming tert. stibines which may be characterized as the corresponding dibromides. The preparation of C₆H₅SbNa₂ and its reaction with C₂H₅Br, Cl(CH₂)₄Cl and C₆H₅(Cl)C?N? N?C(Cl)C₆H₅ are described.     

Derivatives of M(η5-C5H5)2 (M = Mo,W) with alkenylpyridines and related ligands

Reactions of ligands 2-vinylpyridine 1, 4-vinylpyridine 2, 2-allylpyridine 3, 1-allylpyrazole 4, acrylonitrile 5 and allylcyanide 6 with the metallocene derivatives [Mo(η⁵-C₅H₅)₂H₃][PF₆] 7, [Mo(η⁵-C₅H₅)₂HI] 8, [W(η⁵-C₅H₅)₂H₃] [PF₆] 9, [Mo(η⁵-C₅H₅)₂H₂] 10, [M(η⁵-C₅H₅)₂Br₂], M = Mo 11, M = W 12 are described. Reaction of 7 with 1, 8 with 1, 3 with 8 and 4 with 8 gave mixtures of metallocyle isomers resulting from coordination of the nitrogen atom to molybdenum followed by internal hydrometallation; reaction of 11 with 1 gave an olefinic π complex; reaction of either 9 or 11 with 1 gave intractable oils; reactions of 8 with 2, 11 with 5, 12 with 5, 11 with 6 and 12 with 6 yielded monosubstituted products in which the ligand is N-coordinated.     

Darstellung und Eigenschaften von 3-(N,N-Dimethylamino)propyl-Verbindungen des Thalliums

Preparation and Properties of 3-(N,N-Dimethylamino)propyl Thallium Compounds TlCl₃ reacts with Me₂NCH₂CH₂CH₂Li in molar ratio 1:2 with formation of (Me₂NCH₂CH₂CH₂)₂TlCl ( 1 ) which can be transfered with MeLi into (Me₂NCH₂CH₂CH₂)₂TlMe ( 2 ) and with excess of Me₂NCH₂CH₂CH₂Li into (Me₂NCH₂CH₂CH₂)₃Tl ( 3 ) respectively. Comproportionation of 1 with TlCl₃ yields rather instable Me₂NCH₂CH₂CH₂TlCl₂ ( 4 ) from which Me₂NCH₂CH₂CH₂TlMe₂ ( 5 ) can be obtained by alkylation with MeLi. 1–3 and 5 were characterized by elemental analysis, mass spectra, ¹H- and ¹³C-n.m.r. spectra.     

Amidometallate von Lanthan und Gadolinium und Umsetzung von Lanthan,Gadolinium und Scandium mit Ammoniak

Amidometallates of Lanthanum and Gadolinium and the Conversion of Lanthanum, Gadolinium, and Scandium with Ammonia By reaction of the metals with NsNH₂ and NH₃ in the hightemperature- autoclave Na₃[La(NH₂)₆], Na₃[Gd(NH₂)₆], and Na[Gd(NH₂)₄] were prepared, but not any compound of Sc. By corresponding experiments with NH₄I only La(NH₂)₃, GdN, and ScH₂ were obtained. Na₃[La(NH₂)₆] and Na₃[Gd(NH₂)₆] are isotypic with Na₃[Y(KH₂)₆], Na[Gd(NH₂)₄] with Na[Yb((NH₂)₄]. The thermal behaviour of the prepared amides was characterized by DTA and tensimetry.     

Fast orthometalation reactions at a binuclear dirhodium(II) complex. Synthesis,crystal structure and reactivity of Rh2(O2CCH3)3[(C6H4)PPh2]·(HO2CCH3)2

From the reaction of Rh₂(O₂CCH₃)₄(MeOH)₂, in hot acetic acid with PPh₃ the monometalated intermediate Rh₂(O₂CCH₃)₃[(C₆H₄)PPh₂](HO₂CCH₃)₂ has been isolated and characterized by an X-ray study. This compound rapidly reacts with an excess of PPh₃ in dichloromethane at room temperature to give Rh₂(O₂CCH₃)₂-[(C₆H₄)PPh₂]₂(PPh₃)₂ with a head-to-tail structure. The same procedure at higher temperatures gives a mixture of this compound and another doubly metalated compound with a head-to-head structure.     

Die Reaktionen von Benzoylierungsmitteln mit Phosphoriger Säure

Reactions of Benzoylating Agents with Phosphorous Acid H₃PO₃ reacts with (C₆H₅CO)₂O to yield C₆H₅C(OH)(PO₃H₂)₂ 1 . In contrast, the reaction with C₆H₅COCl proceeds with the formation of C₆H₅CCl(PO₃H₂)₂ 2 and p-ClC₆H₄CH(PO₃H₂)₂ 3 . The best yields of 2 and 3 are obtained, if the reaction are carried out under pressure. 2 is rapidly hydrolysed in alkaline solution at elevated temperatures to 1 .     

Substitutionsreaktionen mit Schwefeldiimiden

Substitution Reactions with Sulphur Diimides Substituted sulphur diimides are obtained by the reactions of (CH₃)₃Si? N?S?N? Si(CH₃)₃ with CH₃SO₂Cl and CCl₃SCl or with P₂O₃F₄ and (CH₃)₃Si? N?S?N? SN(CH₃)₂. S₄N₄ reacts with (CH₃)₂Si[N(CH₃)₂]₂ to from (CH₃)₂Si(N(CH₃)₂)? N?S?N? SN(CH₃)₂ while S₃N₂Cl₂ yields (CH₃)₂Si(Cl)? N?S?N? SN(CH₃)₂. It is possible to substitute the chlorine atom by diethylamine in the last compound. The new compounds are intermediates for the syntheses of cyclic sulphur-nitrogen compounds. They were characterized by mass-, ir-, ¹H-nmr spectra and elemental analysis.     

Synthese und Struktur von Ammin- und Amidokomplexen des Iridiums

Synthesis and Structure of Ammine and Amido Complexes of Iridium The reaction of (NH₄)₂[IrCl₆] with NH₄Cl at 300 °C in a sealed glass ampoule yields the iridium(III) ammine complex (NH₄)₂[Ir(NH₃)Cl₅], which crystallizes isotypically with K₂[Ir(NH₃)Cl₅] in the orthorhombic space group Pnma with Z = 4, and a = 1350.0(2); b = 1028.5(3); c = 689.6(2) pm. The reaction of (NH₄)₂[IrCl₆] with NH₃ at 300 °C, however, gives the already known [Ir(NH₃)₅Cl]Cl₂ beside a small amount of [Ir(NH₃)₄Cl₂]Cl₂. In pure form [Ir(NH₃)₅Cl]Cl₂ is obtained by ammonolysis of (NH₄)₂[Ir(NH₃)Cl₅] at 300 °C with NH₃. [Ir(NH₃)₄Cl₂]Cl₂ crystallizes triclinic (P1, Z = 1, a = 660,2(3); b = 680,4(3); c = 711,1(2) pm; α = 103,85(2)°, β = 114,54(3)°, γ = 112,75(2)°). The structure contains Cl^– anions and [Ir(NH₃)₄Cl₂]²⁺ cations with a trans position of the Cl atoms. Upon reaction of [Ir(NH₃)₅Cl]Cl₂ with Cl₂ one ammine ligand is eliminated yielding [Ir(NH₃)₄Cl₂]Cl, which is transformed to orthorhombic [Ir(NH₃)₄(OH₂)Cl]Cl₂ (Pnma, Z = 4, a = 1335,1(3); b = 1047,9(2); c = 673,4(2) pm) by crystallization from water. In the octahedral complex [Ir(NH₃)₄(OH₂)Cl]²⁺ the four ammine ligands have an equatorial position, whereas the Cl atom and the aqua ligand are arranged axial. Oxidation of (NH₄)₂[Ir(NH₃)Cl₅] with Cl₂ at 330 °C affords the tetragonal Ir^IV complex (NH₄)[Ir(NH₃)Cl₅] (P4nc, Z = 2, a = 702.68(5); c = 912.89(9) pm). Its structure was determined using the powder diagram. Oxidation of (NH₄)₂[Ir(NH₃)Cl₅] with Br₂ in water, on the other hand, gives (NH₄)₂[IrBr₆] crystallizing in the K₂[PtCl₆] type. Oxidation of (PPh₄)₂[Ir(NH₃)Cl₅] with PhI(OAc)₂ in CH₂Cl₂ affords the Ir^V amido complex (PPh₄)[Ir(NH₂)Cl₅].     

Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.     

Zur kenntnis nichtmetallischer iminverbindungen : LXVIII . 2,4,1η5,3η3-diazadiphosphetidin,ein phosphorstickstoff-vierring mit 3- und 5-bindigem phosphor

The complex Mo(CO)₂L₂ [L = S₂CNEt₂] reacts with acetylenes to yield both Mo(CO)(RC₂R')L₂ and Mo(RC₂R')₂L₂, with diazenes giving Mo(RN₂R')L₂ and Mo(RC₂R')₂L₂, with diazenes giving Mo(RN₂R')L₂ and Mo(RN₂R')₂L₂, and with CO and PPh₃ to form Mo(CO)₃L₂ and Mo(CO)₂(PPh₃)L₂.     

Models of surface-confined metallocene derivatives

The silsesquioxane [((C₆H₁₁)₇Si₇O₉)(OH)₃] (LH₃) was reacted with [M(C₅H₅)₂Cl₂] (M = Ti, Zr, Hf) and with [Ti(C₅H₅)Cl₃]. The reaction with [Ti(C₅H₅)Cl₃] produced [Ti(C₅H₅)L], whereas the reaction with [Ti(C₅H₅)₂Cl₂] produced a mixture of [Ti(C₅H₅)L]_n. (n = 1, 2) as determined by NMR spectroscopy. Only [Ti(C₅H₅)L] could be isolated from the mixture. The reaction with [M(C₅H₅)₂Cl₂] (M = Zr, Hf) produced oligomeric species which contained no cyclopentadienyl ligands and which were formulated as containing trimeric [M₃L₄Cl]⁻ anions on the basis of analytical and spectroscopic data.