Zeitschrift für ChemieVolume 2, Issue 11 p. 342-342 Kurze Originalmitteilungen Koordinationsverbindungen von Aluminiumtrialkylen mit ditertiären Aminen W. Brüser, W. Brüser Chemisches Institut der Technischen Hochschule Otto von Guericke MagdeburgSearch for more papers by this authorK.-H. Thiele, K.-H. Thiele Chemisches Institut der Technischen Hochschule Otto von Guericke MagdeburgSearch for more papers by this authorH. K. Müller, H. K. Müller Chemisches Institut der Technischen Hochschule Otto von Guericke MagdeburgSearch for more papers by this author W. Brüser, W. Brüser Chemisches Institut der Technischen Hochschule Otto von Guericke MagdeburgSearch for more papers by this authorK.-H. Thiele, K.-H. Thiele Chemisches Institut der Technischen Hochschule Otto von Guericke MagdeburgSearch for more papers by this authorH. K. Müller, H. K. Müller Chemisches Institut der Technischen Hochschule Otto von Guericke MagdeburgSearch for more papers by this author First published: November 1962 https://doi.org/10.1002/zfch.19620021113Citations: 7AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article.Citing Literature Volume2, Issue11November 1962Pages 342-342 RelatedInformation

The crystalline lithium N,N'-diorganoamidinates Li[PhC(NR)(2)] (1: R = c-C6H11, 2: R = iPr) and Li[(CF3)(3)C6H2C-(N-c-C6H11)(2)] (3) have been obtained by the reaction of phenyllithium or 2,4,6-tris(trifluoromethyl)phenyllithium, resp., with diorganocarbodiimides R-N=C=N-R (R = c-C6H11, iPr). These amidinates have been used for the synthesis of the homoleptic lanthanide(Ill) amidinates [PhC(N-c-C6H11)(2)](3)Ln (4-6: Ln = Pr, Nd, Sm) and [PhC(NiPr)(2)](3)Pr (7). Seven-coordinate Lewis-base adducts of the type [PhC(NSiMC3)(2)](3)Ln(NCPh) (8,9: Ln = Sm, Eu) have been prepared by addition of benzonitrile to the homoleptic precursors [PhC(NSiMe3)(2)](3)Ln. The compounds 2 (as its THF adduct), 4, 6, 8 and 9 have been structurally characterized by single crystal X-ray analyses.

The preparation and structural characterization of scandium and f-element complexes derived from the disiloxanediolate dianion, [(Ph2SiO)2O]2-, are reported. Reactions of in situ prepared Ln[N(SiMe3)2]3 (Ln = Eu, Sm, Gd) with (Ph2SiOH)2O in different stoichiometries afforded the lanthanide disiloxanediolates [Eu[[(Ph2SiO)2O]Li(Et2O)]3] (1), [[[(Ph2SiO)2O]Li(dme)]2SmCl(dme)] (2), and [[[((Ph2SiO)2O]Li(thf)2]2GdN(SiMe3)2] (3). In situ formed (Ph2SiOLi)2O reacted with anhydrous NdBr3 (molar ratio 3:1) to give polymeric [[Nd[(Ph2SiO)2O]3[mu-Li(thf)]2[mu2LiBrLi(thf)(Et2O)]]n] (4). Treatment of 3 with Ph2Si(OH)2 in the presence of acetonitrile yielded the dilithium trisiloxanediolate derivative [[Ph2Si(OSiPh2O)2][Li(MeCN)]2]2 (5), which according to an X-ray analysis displays an Li4O4 heterocubane structure. The trinuclear scandium complex [[[(Ph2SiO)2O]Sc(acac)2]2Sc(acac)] (6) was obtained by reaction of [(C5Me5)Sc(acac)2] (C5Me5 = eta5-pentamethylcyclopentadienyl) with (Ph2SiOH)2O in a 3:2 molar ratio. Selective formation of the colorless uranium(VI) derivative [U[Ph2Si(OSiPh20)2]2[(Ph2SiO)2O]] (7) was observed when uranocene, U(eta8-C8H8)2, was allowed to react with (Ph2SiOH)2O. An X-ray diffraction study of the solvated derivative [U[Ph2Si(OSiPh2O)2]2[(Ph2SiO)2O]].Et2O.TMEDA (TMEDA= N,N,N',N'-tetramethyl-ethylenediamine) (7a) revealed the presence of both the original [(Ph2SiO)2O]2- dianion as well as the ring-enlarged [Ph2Si(OSiPh2O)2]2- ligand in the same molecule.

The new anionic sandwich complexes [Li(THF)4][Ln(COT+)2](1–5, Ln = Ce, Pr, Nd, Sm, Y) have been prepared by treatment of anhydrous lanthanide trichlorides with two equivalents of Li2COT∗ [COT∗ = C8H6(SiMe3)2−1,4]. Ion exchange of 4 with [PPN]Cl affords the derivative [PPN][Sm(COT∗)2] (6). Similarly, the hexasilylated sandwich salt [K(THF)3][Tb(COT∗∗)2] (7) [COT∗∗ = C8H5(SiMe3)3-1,3,6] has been obtained by reacting anhydrous TbCl3 with K2COT∗∗ in a 1:2 molar ratio. The molecular structure of 4 has been determined by X-ray diffraction.

2,6-Bis(chlormethyl)pyridine (1) reacts with 4 equivalents of indenyllithium with formation of 2,6-bis(methylenindenyl)pyridine-dilitihium (2) from which with MCl4 . 2thf (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, H-1 n.m.r., ms, ir, and raman spectra. N --> M interactions are discussed.

Depending on the reaction conditions and the ionic radius of the lanthanide ion, tetraphenyldisiloxanediol, (Ph2SiOH)2O, reacts with [Ln{N(SiMe3)2}3{LiCl(thf)3}3] (Ln = Eu, Gd, Sm) to afford novel heterobimetallic rare earth disiloxanediolates, some of which can be regarded as ‘inorganic lanthanide metallocenes’; a ring expanded uranium(VI) derivative, [U{Ph2Si(OSiPh2O)2}2{(Ph2SiO)2O}] 4, is formed upon treatment of uranocene, [U(η8-C8H8)2], with (Ph2SiOH)2O.

Treatment of Ti(NtBu)Cl-2(py)(2) (1, py = pyridine) with bulky heteroallylic ligands in a 1:1 molar ratio affords the monosubstituted derivatives [PhC(NSiMe3)(2)]Ti(NtBu)Cl(py)(2) (2), [Me-OC6H4C(NSiMe3)(2)]Ti(NtBu)Cl(py) (3), and [Ph2P(NSiMe3)(2)]-Ti(NtBu)Cl(py) (4). Similarly, 2:1 reactions afforded the disubstitution products [PhC(NiPr)(2)](2)Ti(NtBu) (py) (6) and [Ph2P(NSiMe3)(2)](2)Ti(NtBu) (7). The bis(pyridine) adduct Ph2P(NSiMe3)(2)Li(py)(2) (5) was isolated as a by-product during the preparation of 4. The molecular structures of 7 has been established by X-ray crystallography.

The preparation of a new benzamidinate ligand containing the nonafluoromesityl substituent is reported. Li[RFC(N-c-C6H11)(2)] (Ib) is prepared by addition of RFLi to N,N'-dicyclohexylcarbodiimide (R-F = nonafluoromesityl). Treatment of ZrCl4 with two equivalents of 1b results in the formation of the zirconium dichloride derivative [RFC(N-c-C6H11)(2)](2)ZrCl2 (2). The related ligand Li[RFC(NSiMe3)(2)] (la) has been used to prepare the corresponding tin(ll) and lead(ll) derivatives. The complexes [RFC(NSiMe3)(2)](2)M (3: M = Sn, 4: M = Pb) have been synthesized and spectroscopically characterized.

AbstractAt reaction of Mn(acac)3 with NaC5H5 in tetrahydrofuran solution Na[Mn(η1−C5H5)4−n(η5 ‐C5H5)n] was obtained as a crystalline, red‐violet, diamagnetic organomanganese(III) compound, which was characterized by n.m.r., i.r., and electronic spectra and by conductivity measurements.

AbstractBis(1‐norbornyl)‐, Bis(2‐norbornyl)‐ und Bis(7‐norbornyl)‐zinkNorbornyl = Bicyclo‐[2.2.1]‐heptyl, (Nor). wurden aus Zinkchlorid und den entsprechenden Grignardverbindungen bzw. Norbornyllithiumverbindungen synthetisiert. Die drei Substanzen unterscheiden sich beträchtlich in ihren Eigenschaften. Eine nähere Charakterisierung erfolgte durch Aufnahme und Auswertung der Massen‐, IR‐ und 13C‐NMR Spektren sowie durch Untersuchung des thermischen Zerfalls und von Komplexbildungsreaktionen.Für Vergleichszwecke wurde das Bis(7‐norbornenyl)‐zinkNorbornenyl = Bicyclo‐[2.2.1]‐hepten(2)‐yl. dargestellt und untersucht.

AbstractDie IR‐ und Raman‐Spektren der Verbindungen OVCl2O–i‐C3H7, OVCl(O–i‐C3H7)2 und OV (O–i‐C3H7)3 sowie die IR‐, Raman‐, 1H‐NMR‐ und 13C‐NMR‐Spektren von OV(O–t‐C4H9)3 werden mitgeteilt. Aus den Spektren geht hervor, daß die Verbindungen als Gleichgewichtsgemische von Rotationsisomeren vorliegen. Für das Tri‐t‐butylorthovanadat im festen Zustand werden die zwischen den Rotationsisomeren auftretenden Enthalpiediefferenzen aus der Temperaturabhängigkeit der Ramanintensitäten abgeschätzt.

AbstractEs wird berichtet über die Synthese, die Eigenschaften sowie die IR‐, 1H‐NMR‐ und Massenspektren von Bis‐4‐methoxybutylzink, (CH3OCH2CH2CH2CH2)2Zn und von Bis‐3‐äthylmercaptopropylzink, (C2H5SCH2CH2CH2)2Zn. Beide Verbindungen liegen vorwiegend in der offenkettigen Form vor. Eine Ausbildung von Chelatringen konnte nur in untergeordnetem Maße nachgewiesen werden.

Die Ergebnisse der IR- und RAMAN-Spektren des Bortriallyls, -tricrotyls und -trimethallyls sowie derer Pyridinkomplexe werden angegeben und die Schwingungsfrequenzen zugeordnet. Bei der Diskussion der Ergebnisse werden die entsprechenden Daten des Bortriathyls zu Vergleichszwecken mit einbezogen. Spectroscopic Investigation of Allylboron Compounds The data of the IR and RAMAN spectra of triallyl-, tricrotyl- and trimethallyl-boron and their coordination compounds are listed and the vibrations assigned. In the discussion of the results data of tri-ethylboron are included.

Bortribenzyl reagiert mit Wolfram(VI)-chlorid zu instabilem Benzylwolframpentachlorid, wahrend mit anderen Benzylierungsmitteln nur wenig definierte Reduktionsprodukte entstehen. – Aus WCl4 · 2 THF und Magnesiumdibenzyl konnte das bei Raumtemperatur stabile Wolframtetrabenzyl gewonnen werden, das eingehend charakterisiert wurde. 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.

Tetrabenzylthorium can be obtained in crystalline form by interaction of benzyllithium with thorium tetrachloride. All properties of the compound indicate σ-bonds between the metal atom and the benzyl groups. The IR spectrum of tetrabenzylthorium is discussed together with that of tetrabenzylzirconium.

Abstract Tetrabenzylthorium can be obtained in crystalline form by interaction of benzyllithium with thorium tetrachloride. All properties of the compound indicate σ-bonds between the metal atom and the benzyl groups. The IR spectrum of tetrabenzylthorium is discussed together with that of tetrabenzylzirconium.

AbstractEs wird über Reaktionen des Vanadinoxidtrichlorids mit Organylverbindungen des Zinks, Quecksilbers und Zinns berichtet. Dabei konnte das Phenylvanadinoxiddichlorid bei tiefer Temperatur in kristalliner Form isoliert und durch das UV‐ und IR‐Spektrum sowie durch die Bildung eines Dipyridylkomplexes charakterisiert werden.

A method for the preparation of tetrabenzyltitanium and some properties of this compound are reported. Particularly a structure for tetrabenzyltitanium is proposed on the basis of its IR spectrum.

AbstractDie Einwirkung von Bortrimethyl auf N,N,N′,N′‐Tetramethyläthylendiamin, N,N,N′,N′‐Tetraäthyläthylendiamin und 2,2′‐Dipyridyl wurde untersucht. Während mit den Äthylendiaminderivaten farblose, kristalline 2:1‐Komplexe entstehen, verhält sich das Bortrimethyl gegenüber 2,2′‐Dipyridyl inert.

Abstract1,4‐Dioxan, N‐Methylmorpholin und N, N′‐Dimethylpiperazin addieren je zwei Molekeln Aluminiumtrimethyl zu kristallinen 1:2‐Komplexen. Aus den gleichen Liganden und Aluminiumtrimethyl lassen sich außerdem definierte 1:1‐Addukte in kristalliner Form erhalten. Die Koordinationsverhältnisse in diesen Verbindungen werden untersucht und diskutiert.Bei der Einwirkung von 2,2′‐Dipyridyl und 1,10‐Phenanthrolin auf Aluminiumtrimethyl entstehen nur 1:1‐Komplexe, in denen das Aluminiumatom mit großer Wahrscheinlichkeit die Koordinationszahl „5”︁ besitzt.