Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XIV. Untersuchungen über Benzylwolframverbindungen-Darstellung und Charakterisierung des Wolframtetrabenzyls

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XIV. Investigations on Benzyl Tungsten Compounds. – On the Formation and Characterization of Tetrabenzyl Tungsten Unstable benzyl tungsten pentachloride is formed from tribenzyl boron and tungsten hexachloride. Other benzylating agents yield only less defined reduction products. – Reacting WCl₄ · 2 THF with dibenzyl magnesium W(CH₂C₆H₅)₄ can be obtained. The new compound is stable at room temperature and is thoroughly characterized.     

Beiträge zur Chemie der Alkylverbindugen von Übergangsmetallen. XXIX. Dibenzylmangan – Darstellung und Reaktionen

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXIX. Dibenzyl Manganese – Preparation and Reactions Manganese(II) acetylacetonate reacts with tribenzyl aluminium and dibenzyl magnesium forming the yellow complexes 3(C₆H₅CH₂)₂Mn · Al(acac)₃ and (C₆H₅CH₂)₂Mn · Mg(acac)₂ Dibenzyl manganese is also formed at the reaction of dibenzyl magnesium or benzyl magnesium chloride with MnCl₂ · 1.5 THF and was separated as the dioxan complex (C₆H₅CH₂)₂Mn · 2C₄H₈O₂, the ligands of which can be removed to a great extent in vacuum. Dibenzyl manganese reacts with CO₂, CS₂ and SO₂ with insertion into the Mn–C-bonds. The corresponding manganese compounds were isolated and furtherly characterized.     

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.     

Beiträge zur Organolanthanidchemie. II. Cylopentadienyllanthanid-1,3-butadien-Komplexe – Darstellung,Eigenschaften und Reaktionen

Contributions to Organolanthanide Chemistry. II. Cyclopentadienyllanthanide 1,3-Butadiene Complexes – Synthesis, Properties, and Reactions From cyclopentadienyllanthanide dihalides and “magnesium butadiene” Cp*La(C₄H₆) · MgI₂ · 3 THF ( I ), Cp*Ce(C₄H₆) · MgBr₂ · 2 THF ( II ), Cp*Nd(C₄H₆) · MgCl₂ · 2 THF ( III ), (1,3-(t-C₄H₉)₂C₅H₃)Nd(C₄H₆) · MgCl₂ · 2 THF ( IV ), CpEr(C₄H₆) · MgCl₂ · 2 THF ( V ) and (1,3-(t-C₄H₉)₂C₅H₃)Lu(C₄H₆) · MgCl₂ · 2 THF ( VI ) were obtained as highly air sensitive complexes which react easily with proton active compounds and molecules with multible bonds. The reaction products with diphenylamine and carbon dioxide Cp*Nd(NPh₂)₂ · NHPh₂ ( VII ) and Cp*Ce(O₂CC₄H₆CO₂) ( VIII ) are discribed. I–VIII were characterized by elementary analysis, i.r., ¹H and ¹³C n.m.r., and EI-MS spectra.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XVIII. Darstellung und Eigenschaften von Vanadintetrabenzyl und von Benzyltantalchloriden

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XVIII. On the Preparation and Properties of Tetrabenzyl Vanadium and Benzyl Tantalum Chlorides Pure tetrabenzyl vanadium was isolated and characterized by elementary analyses, EPR and ¹H-NMR spectra, by hydrolysis and thermal decomposition. — Experiments for the preparation of tetra or pentabenzyl compounds of niobium and tantalum failed, but we could prepare C₆H₅CH₂TaCl₄, (C₆H₅CH₂)₂TaCl₃, and (C₆H₅CH₂)₃TaCl₂, the last two in form of bipyridyl complexes.     

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. 60. Darstellung und Eigenschaften von Zirconocendibenzylen — Molekülstruktur von (Me3SiC5H4)2Zr(CH2C6H5)2

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 60 Synthesis and Properties of Zirconocene Dibenzyl Compounds — Molecular Structure of (Me₃SiC₅H₄)₂Zr(CH₂C₆H₅)₂ It is reported about the synthesis and n.m.r. spectroscopic characterization of zirconocene dibenzyl compounds with substituted cyclopentadienyl rings and the influence of the substituents on the Zr? CH₂ bonds. The molecular structure of (Me₃SiC₅H₄)₂Zr · (CH₂C₆H₅)₂ is reported and discussed.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXVII. Darstellung von Titanacetaten aus Tetramethyl- und Tetrabenzyltitan

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXVII. Preparation of Titanium Acetates from Tetramethyl and Tetrabenzyl Titanium (CH₃)₄Ti reacts with CH₃COOH at deep temperature to the colourless Ti(OCOCH₃)₄. Using ClCH₂COOH slight violet Ti(OCOCH₂Cl)₄ is formed containing small amounts of reduction products. A complete reduction occurs in the analogous reaction with CF₃COOH yielding dark green Ti(OCOCF₃)₃. From (C₆H₅CH₂) 4 Ti and CH₃COOH a green titanium(III,IV) acetat of the formula 4 Ti(OCOCH₃) · Ti(OCOCH₃)₄ was obtained. – The isolated titanium acetates were characterized by elementary analyses, magnetic moments and i.r. spectra.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 50. Eine ungewöhnliche Organolanthanverbindung

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 50. A non-common Organolanthanum Compound Lanthanum reacts with dibenzyl mercury in tetrahydrofuran as a solvent with splitting of solvent molecules and with formation of ethylene and a benzyl hydrido vinyloxide lanthanum complex of the composition C₆H₅CH₂La(H)OCH?CH₂ · 2 THF. This complex, primary well soluble in tetrahydrofuran, is extremely sensitive against air and moisture and undergoes a fast coordination polymerisation with a strong decrease of the solubility. The compound was characterized by elementary analysis, the hydrolysis and deuterolysis reaction, and by the i.r. spectra.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 55. Darstellung und Eigenschaften von Niobocenium- und Tantalocenium-Salzen – Kristall- und Molekülstruktur von [(C5H5)2NbCl2][BF4] · CH3CN

Contributions to the Chemistry of Organo Transition Metal Compounds. 55. Preparation and Properties of Niobocenium and Tantalocenium Salts — Crystal and Molecular Structure of [(C₅H₅)₂NbCl₂][BF₄] · CH₃CN Niobocenium and tantalocenium compounds of the type [(C₅H₅)₂MCl₂]X (X = BF₄, PBh₄, PF₆) were synthesized from the metallocene dichlorides and ferricenium salts, [(C₅H₅)₂Fe]X, in methylene dichloride or tetrahydrofuran. With acetonitrile as solvent [(C₅H₅)₂MCl₂]X · CH₃CN complexes are formed. Stable methyl compounds of the type [(C₅H₅)₂M(CH₃)₂]X were obtained, when (C₅H₅)₂Ta(CH₃)₂ is oxidized by means of ferricenium salts. The new complexes were characterized by elemental analysis, i. r., and ¹H n.m.r. spectra. The structure of [(C₅H₅)₂NbCl₂][BF₄] · CH₃CN has been determined by X-ray structure analysis. The compound crystallizes in the orthorhombic space group Cmcm with a = 8.324(12), b = 19.581(13), c = 9,563(8) Å and Z = 4. The coordination geometry of the Nb atom is tetrahedrally.     

Arylvanadin(III)-Verbindungen,III. Darstellung und Eigenschaften von Triarylvanadin-Verbindungen

Arylvanadium(III) Compounds. III. Preparation and Properties of Triaryl Vanadium Complexes The synthesis of triarylvanadium compounds, VR₃ (R = C₆H₅; 2,6-(CH₃)₂C₆H₃; 2,4,6-(CH₃)₃C₆H₂; (CH₃)₅C₆) is investigated. Only the compounds V[2,6-(CH₃)₂C₆H₃]₃ and V[2,4,6-(CH₃)₃C₆H₂]₃ (crystallized with tetrahydrofuran) are obtained. The complexes V(C₆H₅)(dipy)₂ · THF, V[2,4,6-(CH₃)₃C₆H₂]₃ · Do (Do = py, dipy) are described too.     

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.     

Beiträge zur chemie des bors LXXX. Pentacarbonylchromkomplexe von diorganylmethylthioboranene und von 2-diäthylboryl-5-methylthiophen

Substitution of THF by diorganylmethylthiboranes in (CO)₅Cr · THF yields the rather unstable complexes (CO)₅Cr · CH₃SBR₂ (R = CH₃, C₆H₅). In contrast to the σ-thiophene complex (CO)₅Cr · SC₄H₄ the pentacarbonylchromium complex of the σ-S-bonded 2-diethylboryl-5-methylthiopene is quite stable due to interaction of the boryl group with CO ligands.     

Elektronenreiche Phenylkomplexe der Übergangsmetalle. II. Li4Co2(C6H5)4 · 4THF,Li4Co2(C6H5)4 · 3 Dioxan und Li3Co(C6H5)2(LiC6H5) · 5THF,die ersten Komplexe mit einer Bis(phenyl)cobalt(0)- und -cobalt(-I)-Einheit

Electron-rich Phenyl Complexes of Transition Metals. II. Li₄Co₂(C₆H₅)₄ · 4THF, Li₄Co₂(C₆H₅)₄ · 3 Dioxan and Li₃Co(C₆H₅)₂(LiC₆H₅) · 5THF, the First Complexes with a Bis(phenyl)-cobalt(0)- and -cobalt(-I) Unity . Li₂Co^II(C₆H₅)₄ · 4THF reacts spontaneously in benzene by splitting off of two phenyl radicals to a dimeric bis(phenyl) cobalt(0) complex which has been isolated as a THF and a dioxan adduct Li₄Co₂(C₆H₅)₄ · 4THF and Li₄Co₂(C₆H₅)₄ · 3 Dioxan, respectively. Reduction with lithiumphenyl in ether gives a phenyl cobalt(-I) complex Li₄Co(C₆H₅)₃ · 5THF containing besides σ-bonded phenyl anions lithium phenyl coordinated to cobalt in a π-complex like manner, proved by means of ¹³C? NMR-spectroscopy. The stabilization of the low oxidation states is explained by coordination of the lithium ions to cobalt by multiple center bonds, and for each compound a plausible structure is derived.     

Chemie polyfunktioneller liganden: LXXIII. Synthese,struktur und reaktionsverhalten von cryptanden (bzw. spheranden) mit den heteroelementen arsen,sauerstoff, schwefel und stickstoff

The reaction of N(CH₂CH₂Cl)₃ (I) with KAs(C₆H₅)₂·dioxane ($\text{1}\text{2}$) in THF yields, as Sacconi et al. reported earlier, 80% of N[CH₂CH₂As(C₆H₅)₂]₃ (II). II is now obtained in a still higher quantity from the reaction of [HN(CH₂CH₂Cl)₃]Cl (III) with NaAs(C₆H₅)₂ in liquid ammonia. Treatment of II with gaseous HI in dry CH₂Cl₂ results in the formation of [HN(CH₂CH₂AsI₂)₃]I (IV), which is isolated by recrystallisation from THF as [HN(CH₂CH₂AsI₂)₃]I · THF ($\text{1}\text{1}$) (IVa). IVa reacts with H₂O/NH₃ or H₂S/N(C₂H₅)₃ to give the novel cryptands [N(CH₂CH₂)₃]₈-(As₄O₄)₆ (V) or [N(CH₂CH₂)₃]₈(As₄S₄)₆ (VI), which also can be denoted as spherands. The reaction of V with dry gaseous HCl in benzene leads to [HN(CH₂-CH₂AsCl₂)₃]Cl (VII). All the new compounds are characterized, as far as possible, by their IR, FIR, Raman, ¹H NMR and mass spectra. To determine the structure of V a single X-ray crystal study was carried out. Moreover II, which is already well-known but not completely characterized, is included in this discussion only for spectroscopic comparison.     

Beiträge zur Chemie der Alkylverbindungen von übergangsmetallen. XXXI. Darstellung und Eigenschaften von Benzylmangannitrosyl,C6H5CH2Mn(NO)

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXI. Preparation and Properties of Benzyl Manganese Nitrosyl, C₆H₅CH₂Mn(NO) (C₆H₅CH₂)₂Mn reacts with NO with formation of dibenzyl and C₆H₅CH₂Mn(NO), which contains the manganese in the valence state 0. The manganese compound was characterized by elementary analysis, molecular weight, magnetic moment, ir-spectrum and the course of the thermal decomposition.     

Innerkomplexe mit Metallamidbindungen. II. Zink- und Chrom(II)-Komplexe des 2-[β-(Phenyl-amino)-äthyl]-pyridins

The preparation of uncharged complexes with metal amide bonds of type [MeN₄]^±0 (Me = Zn²⁺, Cr²⁺ is reported. These compounds are obtained by the interaction between Zn(C₆H₅)₂ or Cr(C₆H₅)₃ · 3 THF and 2-[β-(phenyl-amino)-ethyl]-pyridine (I). The same complexes are formed by the reaction between ZnCl₂ · 2 THF, CrBr₂ · 2 THF, or CrCl₃ · 3 THF and the lithium amide (II), which is prepared from (I) and phenyl lithium. The structure of the chromium(II) complex is discussed on the basis of magnetic and visible absorption measurements.     

Strukturen von polaren Magnesiumorganylen: Synthese und Struktur von Basen‐Addukten des Magnesiumindenids

An improved X‐ray structure determination of magnesium indenide Mg(C₉H₇)₂ ( 1 ) at low temperature was carried out. Four donor‐acceptor complexes of Mg(C₉H₇)₂ ( 1 ) with O‐ and N‐donor Lewis bases were synthesized and characterized by X‐ray structure analysis. With dioxane and tetramethylethylenediamine (TMEDA) two simple monomeric complexes, [Mg(C₉H₇)₂(dioxane)₂]·1.5dioxane ( 2a ) and [Mg(C₉H₇)₂(TMEDA)] ( 3 ), were formed. With the O‐donors tetrahydrofuran (THF) and dimethylsulfoxide (DMSO) two ionic magnesium compounds 4 and 5 could be synthesized which have a [MgL₆]²⁺ cation [L = THF and DMSO] and two uncoordinated indenide anions.     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. XXXVIII. Reaktion von Dibenzylmangan mit Sauerstoff

Contributions to the Chemistry of Transition Metal Alkyl Compounds. XXXVIII. Reactions of Dibenzyl Manganese with Oxygene (C₆H₅CH₂)₂Mn · C₄H₈O₂ reacts with oxygen forming an unstable deep violet compound which changes in a stable unsoluble yellow peroxide of the formula C₆H₅CH₂MnO? OMnCH₂C₆ H₅. With excess oxygen a polynuclear complex of 3 valent manganese is formed with the composition Mn₄O₄(OH)₄(OCHC₆H₅)₂. The compounds isolated were characterized by the products of hydrolyses and thermolyses, anaerobic reaction with iodine, magnetic moments, i.r. and e.s.r. spectra.     

Über das Verhalten von Diorganophosphinsäurehalogeniden gegenüber LEWIS-Säuren und LEWIS-Basen

From R₂POCl [R = (CH₃)₂N; C₆H₅] and Ag[SbF₆] in polar solvents, extremely hygroscopic donor-acceptor complexes R₂POF · SbF₅ have been obtained according to equation (1) in ?Inhaltsübersicht”?. The interaction between R₂POCl (R = C₆H₅; CH₃) and the Lewis base KP(C₆H₅)₂ proceeds via a complicated redox mechanism (see equat. (2) in ?Inhaltsübersicht”?) yielding diorganophosphinic anhydride, the mixed diorgano-diphenyl-diphosphine, and tetraphenyl-diphosphine. All these reaction products have been identified by IR-spectroscopic, analytic and other chemical methods.