Die Ammonolyse von Triphenylcyclohexylblei

The Ammonolysis of Triphenylcyclohexyllead The ammonolysis of C₆H₁₁Pb(C₆H₅)₃ in liquid NH₃ in the presence of KNH₂ results in the formation of K[Pb(NH₂)₃]. The organic radicals are eliminated as C₆H₁₂ and C₆H₆ in the course of a redox reaction. The mechanism of the reaction is discussed.     

Über die Ammonolyse von Organometallen. XII. Die Ammonolyse von Dimethyl-diphenyl- und Dimethyl-dibenzyl-silan

Dimethyl-diphenyl and dimethyl-dibenzyl-silane react in liqu. NH₃ in the presence of KKH₂ giving rise to the formation of H₂N? Si(Me₂)? NH? Si(Me₃)? NHK (III); exclusively C₆H₅ and C₆H₅CH₂ are split off and substituted by NH₂. Reaction of the potassium compound III with the equivalent amount of NH₄Cl brings about a mixture of octamethylcyclotetrasilazane and hexamethylcyclotrisilazane.     

Die Ammonolyse von Halogenokomplexen des vierwertigen Platins

Ammonolysis of Halogeno Complexes of Tetravalent Platinum Reactions of liquid ammonia and ammonium hexahalogenoplatinates(IV) at ?40°C yield mixtures of halogenoammine complexes [Pt(NH₃)_6?nX_n]X_4?n (X = Cl, Br, I; n = 3, 2, 1, 0). Hexaammine platinum(IV) salts, [Pt(NH₃)₆]X₄, may be isolated as main product only after several weeks of reaction. Interactions at room temperature of liquid ammonia and hexachloro or hexabromo complexes produce quantitatively the novel dinuclear di-m?-amido-bis[tetraammineplatinum(IV)] complex, [(H₃N)₄Pt(NH₂)₂Pt(NH₃)₄]X₆. By interaction of gaseous or liquid ammonia and subsequent addition of potassium amide solution in excess potassium hexaamido platinate(IV), K₂[Pt(NH₂)₆], is formed in good yield.     

Über Cyanatverbindungen und deren reaktives Verhalten. X. 14N-NMR-Untersuchungen an einigen diamagnetischen Metall- und Triphenylzinnthiocyanatverbindungen sowie Kaliumselenocyanat

Chemical shifts and line-widths of the following soluble diamagnetic ¹⁴N-compounds are given: (NH₄)₂[Hg(SCN)₄], Sr(SCN)₂, K₂[Zn(NCS)₄] · 2 CH₃COCH₃, K₂[Zn(NCS)₄], K₄[Cd(NCS)₆], (C₆H₅)₃SnNCS, C₇H₇NH₃[(C₆H₅)₃Sn(NCS)₂], K[(C₆H₅)₃Sn(NCSe)₂] und KSeCN. Types of bonding of the NCY group (Y = S, Se) in these compounds are discussed and correlated to the measurements. Dependences of the line-widths upon different concentrations and temperatures are given for aqueous KSCN solutions.     

Über Chalkogenolate. LIV. Untersuchungen über Thioameisensäuren 2. Darstellung und Eigenschaften von Dithioformiaten

K[HCS₂] was prepared by interaction of chloroform with K₂S. Rb[HCS₂] and Cs[HCS₂] were formed by reaction of trimeric dithioformic acid with alcoholates (X-ray data see ?Inhaltsübersicht”?). The dithioformates T1[HCS₂], In[HCS₂]₃, and M[HCS₂]₂ with M = Pb, Zn, Cd, Hg, and M[HCS₂] with M = [(C₆H₅)₄P], [(C₆H₅)₄As], [(C₂H₅)₄N], (C₆H₅)₃Sn have been prepared. The prepared compounds are investigated by different methods.     

Über die Ammonolyse des Hexamminkobalt(III)-Ions in flüssigem Ammoniak

[Co(NH₃)₆](NO₃)₃ (I) dissolved in liquid NH₃ reacts with 1 equivalent of KNH₂ forming the trinuclear complex [(H₃N)₄Co(NH₂)₂Co(NH₃)₃NH₂Co(NH₃)₅](NO₃)₅ (II) and the binuclear complex [(H₃N)₄Co(NH₂)₂Co(NH₃)₄](NO₃)₄ (III). The cleavage of II with diluted acetic acid + Na₂SO₄ results in the formation of [(H₃N)₄Co(NH₂)₂Co(NH₃)₃ OH₂](SO₄)₂ · 2 H₂O (IV) and [Co(NH₃)₆]³⁺ isolated as the nitrate I. IV could be transformed to III, which gives trans-[Co(NH₃)₄Cl₂]Cl when reacting with a mixture of conc. HCl and H₂SO₄. From the obtained results one may infer that the ammonolysis of I corresponds to the hydrolysis of hexaquoxomplexes of trivalent cations in the course of which polynuclear complexes are also formed.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 52. Darstellung,Charakterisierung und Reaktionen von (C5H5)3Ce · THF und Na[Ce(C5H5)4] · THF

Contributions to the Chemistry of Organo Transition Metal Compounds. 52. Preparation, Characterization, and Reactions of (C₅H₅)₃Ce · THF and Na[Ce(C₅H₅)₄] · THF (C₅H₅)₃ · THF ( I ) was synthesized in a simple manner by reaction of (NH₄)₂[Ce(NO₃)₆] with C₅H₅Na. With excess C₅H₅Na the complex Na[Ce(C₅H₅)₄] · THF ( II ) could be obtained. In addition of cyclovoltammetric and polarographic measurements it was tried without success to transfer I and II into organocerium( IV ) compounds by means of different oxidizing agents. II reacts with I₂ and (C₆H₅)₃CCl forming Na[(C₅H₅)₃CeI] · THF or Na[(C₅H₅)₂CeI₂] · 4 THF and I besides of (C₆H₅)₃CCl respectively. At interaction of I with Co(acac)₃ the cobalticinium salt [(C₅H₅)₂Co][C₅H₅Ce(acac)₃] is formed. The compounds obtained were characterized by elementary analysis, hydrolysis products, magnetic moments, i.r., ¹H-n.m.r. und u.v.-vis spectra, and measurements of electric conductivity.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XLIII. Über die Reduktion von Organozirconium(IV)-Verbindungen mit Lithiumorganylen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XLIII. Reduction of Organozirconium(IV) Compounds with Lithium Organyls. (C₅H₅)₂ZrR₂ derivatives react with lithium organyls by forming of organozirconium(III) or organozirconium(II) compounds. (C₅H₅)Zr(CH₂C₆H₅)₂ · O(C₂H₅)₂ and (C₅H₅)ZrC₆H₅ · 3 O(C₂H₅)₂ were isolated in a definite form. Informations on the formation of (C₅H₅)Zr(C₆H₅)₂ · 2 O(C₂H₅)₂ could be confirmed. The compounds obtained were characterized by elementary analysis, hydrolysis products, reactions with iodine, magnetic moments, and the IR and EPR spectra.     

Darstellung von Acetatoblei(IV)- und Acetatozinn(IV)- manganpentacarbonylen durch Acidolyse von (C6H5)4–n−M[Mn(CO)5]n (M  Sn,Pb; n = 1, 2) mit Essigsäure

Preparation of Acetatolead(1V) and Acetatotin(1V) Manganese Pentacarbonyls by Acidolysis of (C₆H₅)_4?n M[Mn(CO)₅]_n (M ? Sn, Pb; n = 1, 2) with Acetic Acid By acidolysis of (C₆H₅)_4?nM[Mn(CO)₅]_n (M ? Sn, Pb; n = 1, 2) with acetic acid no M? Mn bonds are broken, but M? C bonds. In this reaction (CH₃COO)₂M[Mn(CO)₅]₂ is formed from (C₆H₅)₂M[Mn(CO)₅]₂, and (CH₃COO)₃SnMn(CO)₅ and (CH₃COO)₂C₆H₅PbMn(CO)₅ from (C₆H₅)₃MMn-(CO)₅. (CH₃COO)₂C₆H₅SnMn(CO)₅ is prepared from Cl₂C₆H₅SnMn(CO)₅ and AgCH₃COO. According to IR spectroscopic data the acetato ligands of the diacetato complexes are bidentate, while in (CH₃COO)₃SnMn(CO)₅ bi- and monodentate carboxylate groups are present. For the central atoms Sn and Pb octahedral coordination is proposed.     

Darstellung von Tetracarbonyl-triphenylphosphinmanganorganoplumbanen R4−nPb[Mn(CO)4P(C6H5)3]n (RCH3, C6H5; n = 1,2)

Preparation of R_4?nPb[Mn(CO)₄P(C₆H₅)₃]_n Compounds (R?CH₃, C₆H₅; n = 1, 2) As the first examples of organolead manganese carbonyls substituted in the manganese carbonyl ligand compounds of the type R_4?nPb[Mn(CO)₄P(C₆H₅)₃]_n (R?CH₃, C₆H₅; n = 1, 2) have been prepared by the alkali salt method from R_4?nPbCl_n and NaMn(CO)₄P(C₆H₅)₃. (C₆H₅)₂Sn[Mn(CO)₄P(C₆H₅)₃]₂ has been gained by the same method and also by thermal ligand exchange. According the IR data the ligand P(C₆H₅)₃ is trans to the tetrahedrally surrounded lead. In solution to compounds are monomeric.     

Template-Reaktion von Bis(acetylacetonato)-dioxo-molybdän(VI) mit Benzoylhydrazin und Triphenylphosphan

Template Reactions of Bis(acetylacetonato)-dioxo-molybdenum(VI) with Benzoylhydrazine and Triphenylphosphane By reaction of MoO₂(acac)₂ with C₆H₅? CO? NH? NH₂ in the presence of P(C₆H₅)₃ Mo(NNCOC₆H₅)((CH₃)₂CNNCOC₆H₅)(P(C₆H₅)) was obtained besides MoO(acac-NNHCOC₆H₅)(NNHCOC₆H₅). The earlier compound was characterized by X-ray structural analysis. Crystallographic data see ?Inhaltsübersicht”?.     

Organozin- und organobleiderivate von N-(2,4-dinitrophenyl)glycin

Organotin and organolead derivatives of N-(2,4-dinitrophenyl)glycine (HDNG), R₃MDNG (M = Sn, Pb; R = CH₃, C₆H₅) and (C₆H₅)₂Pb(DNG)₂, have been prepared from R₃MOH or [(C₆H₅)₂PbO]_n and HDNG, respectively. (CH₃)₃PbDNG was also obtained from (CH₃)₃PbBr and TlDNG. According to spectroscopic data R₃M groups in R₃MDNG are essentially planar and are bridged by bidentate carboxylate groups of DNG. NH does not coordinate to M. Penta-coordination is also indicated by Mössbauer data of R₃SnDNG. Also for (C₆H₅)₂Pb(DNG)₂ a chain structure but with hexacoordination of Pb is proposed. The compounds are monomeric in solution.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXV. Zum Reaktionsverhalten von Tetrabenzyltitan gegenüber Lithiumalkylen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXV. Reactions in Tetrabenzyl Titanium/Alkyllithium Systems Organotitanium(IV) complexes of the type Li[(C₆H₅CH₂)₄TiR] (R = CH₃, C₂H₅, n-C₄H₉) were isolated from tetrabenzyl titanium and lithium alkyls at deep temperature. The reddish brown, crystalline compounds decompose between ?30 and 0°C with formation of benzyltitanates(II) which composition differs between Li₂[Ti(CH₂C₆H₅)₄] and Li[Ti(CH₂C₆H₅)₃]. From these complexes pure dibenzyl titanium can be isolated. The reaction mechanism is discussed. Experiments for isolation of a benzyl titanium(III) compound from (C₆H₅CH₂)₄Ti/RLi systems failed in all cases. Recent informations about stable tribenzyl titanium obtained from tetrabenzyl titanium and ethyl lithium could not be confirmed.     

Die Ammonolyse von (NH4)2GeF6. Darstellung und Struktur von NH4[Ge(NH3)F5]

Ammonolysis Reaction of (NH₄)₂GeF₆. Synthesis and Structure of NH₄[Ge(NH₃)F₅] (NH₄)₂GeF₆ reacts with ammonia to yield NH₄[Ge(NH₃)F₅] at 280°C. The reaction path was elucidated by in situ time and temperature resolved X-ray powder diffraction. NH₄[Ge(NH₃)F₅] crystallizes isostructurally to NH₄[Si(NH₃)F₅] in the tetragonal space group P4/n (No. 85) with lattice constants a = 619.41(1) pm and c = 724.70(1) pm. The germanium atom is coordinated by five fluorine atoms and the nitrogen atom of the ammonia molecule. The ammonium cation is located on the Wyckoff position (2 a) in P4/n. The crystal structure is stabilized by extensive hydrogen bonding.     

Perfluoralkylierte Säuren des Phosphors. III. Diphenyltrifluormethyl- und Diphenyltrifluoracetylphosphinoxid als Zwischenstufen bei der Darstellung von Diphenyl-phosphinsäure-(bis-trifluormethyl-diphenyl-orthophosphinsäure)-anhydrid

Perfluoroalkylated Acids of Phosphorus. III. Diphenyl Trifluoromethyl and Diphenyl Trifluoroacetyl Phosphinic Oxide as Intermediates in the Preparation of Diphenyl Phosphinic Acid(Bis-Trifluoromethyl Diphenyl Orthophosphinic Acid) Anhydride (C₆H₅)₂P(O)CF₃ ( 3 ) and (C₆H₅)₂P(O)C(O)CF₃ ( 2 ) were identified as intermediates in the thermal rearrangement and condensation of (C₆H₅)₂POCOCF₃ by IR-, NMR- and mass spectroscopy. An improved method for the preparation of (C₆H₅)₂P(O)? O? P(C₆H₅)₂(CF₃)₂ is given.     

Über Chalkogenolate. 128. Untersuchungen über Ester der N-Cyancarbamidsäure. 1. Darstellung und Eigenschaften der Ammoniumsalze von N-Cyancarbamidsäureestern und vom N-Methyl-N-cyancarbamidsäureethylester

On Chalcogenolates. 128. Studies on Esters of N-Cyancarbamic Acid. 1. Synthesis and Properties of Ammonium Salts of N-Cyancarbamic Acid Esters and of the Ethyl Ester of N-Methyl N-Cyancarbamic Acid The reaction of NC? N(CO? OR)₂ with NH₃(g) yields NH₄[NC? N? CO? OR], where R = CH₃, C₂H₅, and C₆H₅. NH₄[NC? N? CO? OC₂H₅] reacts with H₃CI to form NC? N(CH₃)? CO? OC₂H₅. The called compounds have been studied with chemical and spectroscopic methods.     

Untersuchungen an Selen-Verbindungen. LXIV. Darstellung und Eigenschaften von Säurederivaten von Phenylselen(IV) -Verbindungen (C6Hs) 2SeX2, (C6H5) 3SeX

Studies on Selenium Compounds. LXIV. Preparation and Properties of Acid Derivatives of Phenylselenium(IV) Compounds (C₆H₅) ₂SeX₂ and (C₆H₅) ₃SeX. Reactions of (C₆H₅) ₂SeBr₂ and (C₆H₅) ₃SeCl with silver salts of acids are investigated. From (C₆H₅) ₂SeBr₃ and AgY (Y = N0₃, CH₃CO₃, CF₃CO₂, 1/2 SO₄, CH₃SO₃, NCO) the compounds (C₆H₅) ₂Se(NO₃) ₂ (C₆H₅) ₂Se(CH₃CO₂) ₂, (C₆H_s) ₂Se(CF₃CO₂) ₂, (C₆H₅) ₂SeSO₄, (C₆H₅) ₂Se(CH₃SO₃) ₂ and (C₆H₅) ₂Se(NCO) ₂ are prepared. They are characterized by solubility, molecular weight and conductivity. Reaction of (C₆H₅) ₃SeCl and AgX (X = NO₃, CH₃CO₂) yields (C₆H₅) ₃SeNO₃ and (C₆H₅) ₃SeCH₃CO₂.     

Water‐soluble and Halogen‐free Hexaammine Complexes of Metal Ions of Group 9 – Synthesis,Crystal Structures,and Vibrational Spectra

Reaction of [M(NH₃)₆]Cl₃ (M = Co, Rh, Ir) and [Ir(NH₃)₅(OH₂)]Cl₃ with (NH₄)₂C₂O₄ · H₂O in aqueous solution resulted in the isolation of [M(NH₃)₆]₂(C₂O₄)₃ · 4 H₂O and [Ir(NH₃)₅(OH₂)]₂(C₂O₄)₃ · 4 H₂O, respectively. The complexes have been characterized by X‐ray crystallography, IR and UV/VIS spectroscopy. The isomorphous compounds crystallize in the orthorhombic space group Pnnm (No. 58). Four molecules of crystal water are involved in an extended three‐dimensional hydrogen bonding network. The librational modes of the lattice water around 600 cm^–1 allow the characterization of [Ir(NH₃)₆]₂(C₂O₄)₃ · 4 H₂O and [Ir(NH₃)₅(OH₂)]₂(C₂O₄)₃ · 4 H₂O, respectively, by IR spectroscopy. The band around 600 cm^–1 shows a significant frequency shift in the IR spectra of the hexaammine and aquapentaammine complex of iridium(III) and, by that, a distinction is possible.     

Synthese und Eigenschaften von Metallocen‐ und Halbsandwich‐Komplexen mit pyridinhaltigen Brücken bzw. Seitenketten

Synthesis and Properties of Metallocene and Half Sandwich Complexes with Pyridine‐containing Bridges or Side Chains 2,6‐Bis(chlormethyl)pyridine ( 1 ) reacts with 4 equivalents of indenyllithium with formation of 2,6bis(methylenindenyl)pyridine‐dilitihium ( 2 ) from which with MCl₄ · 2 thf (M = Zr, Hf) the corresponding metallocene dichlorides 3 and 4 can be obtained. At reaction of 1 with 2 equivalents of C₅H₅Na only one Cl atom is replaced by a C₅H₅Na unit. Following reactions with indenyl lithium and ZrCl₄ · 2 thf give the unsymmetric complex [C₅H₃N–2,6‐CH₂‐(2‐C₅H₄)–(6‐C₉H₆)ZrCl₂] ( 7 ). – Picolylcyclopentadiene ( 8 ) and 1‐(picolyl)‐indene ( 9 ) are synthesized from 2‐chlomethyl‐pyridinium chloride and C₅H₅Na or indenyl lithium respectively, which are transferred in the half sandwich complexes (C₅H₄N–CH₂C₅H₄)MCl₃ (M = Ti 10 , Zr 11 ) and (C₅H₄–CH₂C₉H₆)ZrCl₃ ( 12) . The compounds were characterized by elemental analysis, ¹H n.m.r., ms, ir, and raman spectra. N → M interactions are discussed.     

Equilibrium phase behavior of aqueous two-phase systems containing 17R4/L64 and citrates

The cloud points (CPs) of the copolymers 17R4 and L64 were first measured, and then the effects of salts ((NH₄)₃C₆H₅O₇, K₃C₆H₅O₇) on 17R4 and L64 were researched. After finishing the work described above, the temperature (278.15, 283.15, and 288.15) K of aqueous two-phase systems was determined, which consist of 17R4-(NH₄)₃C₆H₅O₇, 17R4-K₃C₆H₅O₇, L64-(NH₄)₃C₆H₅O₇, and L64-K₃C₆H₅O₇. Finally, the liquid–liquid equilibrium (LLE) data of binodal curve and the tie line for 17R4-(NH₄)₃C₆H₅O₇ aqueous two- phase systems (ATPSs) 17R4-K₃C₆H₅O₇ ATPSs, L64-(NH₄)₃C₆H₅O₇ ATPSs, and L64-K₃C₆H₅O₇ ATPSs were obtained. Nonlinear fitting of the empirical equation was used for making the diagram. The results showed that the change in the size of the two-phase areas increases with the increase of temperature. The capacity of the salts to induce phase segregation follows the Hofmeister series, that is, K₃C₆H₅O₇?>?(NH₄)₃C₆H₅O₇. In addition, the findings also showed that the phase separation ability of 17R4 is better than that of L64.