Ringerweiterungen an Benzochinol-acetaten, 2. Mitt.: Synthese von Troponen aus Benzochinolacetaten; β-Alkylierung des o-Acetoxy-cyclohexadienonsystems; Herstellung von 2-Aminotroponen

Zusammenfassung Ausgehend von Phenolen bestimmter Konstitution kann man mit Hilfe der o-Benzochinol-acetate durch Ringerweiterung mit Diazomethan—Bortrifluorid zu Troponen mit derselben Substituentenfolge gelangen¹. Als Nebenprodukte treten die in Stellung 5 methylierten Chinolacetate und Tropone auf. Durch Variation der Substituenten in Stellung 1 und 5 des o-Cyclohexadienon-systems ist es möglich, die Ringerweiterung oder die Methylierung in Position 5 zur Hauptreaktion zu machen.Einwirkung von Hydrazinhydrat auf das Tropon liefert ein Gemisch aus 2-Amino- und 2-Hydrazinotropon. Hydrogenolyse der Hydrazinoverbindung mitRaney-Nickel gibt in guter Ausbeute die Aminoverbindung.Mit 1 Abbildung1. Mitt.:E. Zbiral, J. Jaz undF. Wessely, Mh. Chem.92, 1155 (1961).     

Die Zersetzungsreaktion des Dialan-Radikalanions [R2Al-AlR2]·− in DME: I. Kristallstrukturen von R2Al(Me)OC2H4OMeK(DME) und R2Al(OC2H4OMe)2K (R  CH(SiMe3) 2)

Tetrakis[bis(trimethylsilyl)methyl]dialane(4) (1) reacts as recently reported with potassium in 1,2-dimethoxyethane (DME) to yield after purification the surprisingly stable radical monoanion [R₂AlAlR₂]·⁻ [K(DME)₃]⁺ (2) (R  CH(SiMe₃)₂). With a longer reaction time of some days at room temperature and an excess of potassium, however, complete decomposition occurs under cleavage of ether molecules and formation of several new products. One of these compounds was identified as R₂AlMe(OC₂H₄OMe)K(DME) (3) and characterized by a crystal structure determination. Two further derivatives were synthesized and their spectroscopic data compared to the decomposition products: R₂Al(OC₂H₄OMe)₂K (6), also characterized by crystal structure determination, and [R₂AlMe₂]⁻ [K(DME)₆]⁺ (9), but due to the NMR characterization only 9 could be a component of the above-mentioned reaction mixture. In both aluminium alcoholates (3 and 6) the potassium ion is bound in a chelating manner by oxygen atoms of the aluminate unit, probably for this reason they are very soluble in non-polar solvents. In the solid state 3 polymerizes by intermolecular K…H₃CAl bridges forming one-dimensional chains along a crystallographic glide plane, and 6 forms dimers via KOK bridges and fourfold coordinated oxygen atoms.     

Koordinationschemie tripodaler Triisocyanid-Liganden: Synthese von Komplexen des Typs CH3C[CH2NC-M(CO)x]3 (M = Cr,W, χ = 5; M = Fe, χ = 4) und Kristallstruktur von CH3C[CH2NC-W(CO)5]3

The triisocyanide ligand CH₃C(CH₂NC)₃, time, reacts with metal carbonyls M(CO)_x (M = Cr, W, χ = 6; M = Fe, χ = 5) to give the triply metal carbonyl substituted complexes CH₃C[CH₂NCM(CO)_x]₃ (M = Cr, W, χ = 5; M = Fe, χ = 4). CH₃C[CH₂NCW(CO)₅]₃ was characterized by an X-ray structure determination.     

The photo-induced decarbonylation of Cp′M(NO)(CO)2 (M = Cr,Mo, W) with diorgano dichalcogenides (R2E2; E = S,Se; R = Me,Ph)

The photo-induced decarbonylation of CpCr(NO)(CO)₂ (1a) in MeCN solution in the presence of R₂E₂ (E = S, Se; R = Me, Ph) leads to the formation of chalcogenolato-bridged binuclear complexes Cp₂Cr₂(NO)₂(-ER)₂ [E = S; R = Me (2a), Ph (3a); E = Se, R = Me (4a), Ph (5a)] while reactions between CpM(NO)(CO)₂ [M = Mo (1b), W (1c)] and Ph₂E₂ (E = S, Se) result in mononuclear complexes CpM(NO)(EPh)₂ [M = Mo; E = S (9b), Se (10b); M = W, E = S (11c), Se (12c)]. The corresponding reactions of (1b) with Me₂E₂ (E = S, Se) yielded both mono and binuclear complexes: CpMo(NO)(SeMe)₂ (8b), Cp₂Mo₂(NO)₂(-EMe)₂ [E = S (6b), Se (7b)]. The new complexes have been characterized by i.r., ¹H-, ¹³C-n.m.r. spectra and by electron-impact mass spectrometry.     

Synthese,Struktur und Reaktivität von funktionalisierten Stibanidokomplexen des Eisens und Rutheniums [(η5-C5Me5)(CO)2MSbR1R2] (M = Fe,Ru; R1, R2 = SiMe3, C(O)tBu,C(O)Ph,C(O)-1 Ad)

Synthesis, Structure, and Reactivity of Functionalized Stibanido Complexes of Iron and Ruthenium [(η⁵-C₅Me₅)(CO)₂MSbR¹R²] (M = Fe, Ru; R¹, R² = SiMe₃, C(O) t Bu, C(O)Ph, C(O)-1 Ad) The reaction of equimolar amounts of [(η⁵-C₅Me₅)(CO)₂RuSb(SiMe₃)₂] ( 1 b ) and the carboxylic chlorides RC(O)Cl (R = tBu, Ph, 1-adamantyl) afforded the acyl(trimethylsilyl)stibanido complexes [(η⁵-C₅Me₅)(CO)₂RuSb · {C(O)R}(SiMe₃)] 2 b (R = tBu), 4 b (R = Ph), and 6 b (R = 1-Ad). The treatment of 1 b with two molar equivalents of pivaloyl chloride and benzoyl chloride led to the diacylstibanido complexes [(η⁵-C₅Me₅)(CO)₂RuSb{C(O)R}₂] ( 3 b , 5 b ). Analogously, the iron complex [(η⁵-C₅Me₅)(CO)₂FeSb · (SiMe₃)₂] ( 1 a ) is converted into the corresponding diacylstibanido complexes 3 a (R = tBu), 5 a (R = Ph) and 7 a (R = 1-Ad) by an excess of acid chloride. The treatment of 1 a with equimolar amounts of RC(O)Cl gave inseparable mixtures of starting material and the monoacyl- and diacyl stibanido complexes. Oxalyl chloride reacted quantitatively with two equivalents of 1 a to give complex [{(η⁵-C₅Me₅) · (CO)₂FeSb(SiMe₃)C(O)}₂] ( 8 ). The molecular structures of 1 a , 2 b and 5 b were elucidated by single crystal X-ray analyses.     

An absolute integrated infrared intensity study of (η6C6H5R)Cr(CO)2(CS) (R = H,Me, Cl,CO2Me)

The absolute integrated i.r. intensities of the CO and CS stretching bands of the thiocarbonyl complexes (η⁶C₆H₅R)Cr(CO)₂(CS), where R = H, Me, Cl and CO₂Me, have been determined in CS₂ solutions. The intensities have been correlated with each other and with the band wavenumbers, and have been shown to be dependent on the nature of the substituent R in the aromatic ring. The intensities have been demonstrated to be better probes of the electronic effects occurring in these complexes than are the wavenumbers, and correlate well with the Hammett substituent parameters, σ⁰.     

Zur Charakterisierung von 1,1,2,3,3-Pentacyanopropenid als Komplexligand in ein- und zweizähniger Funktion. Darstellung von Komplexen des Typs [MX(PPh3)n] (M = CuI,AgI; X = NCC{C(CN)2}2; n = 2, 3)

Pseudoelement Compounds. XII. [1] On the Characterization of 1,1,2,3,3-Pentacyanopropenide in Unidentate and Bidentate Function. Syntheses of Complexes of the Type [MX(PPh₃)_n] (M = Cu^I, Ag^I; X = NCC{C(CN)₂}₂; n = 2, 3) 1,1,2,3,3-Pentacyanopropenide is characterized as unidentate and bidentate ligand. For that reason compounds of the types [MX(PPh₃)₃] ( 6 ) and [MX(PPh₃)₂]₂ ( 8 ) (M = Cu^I, Ag^I) are synthesized. In the complexes 6 the ionic ligand is coordinated unidentately through an end-on nitrile group of a C(CN)₂ unit and in the dimeric complexes 8 bidentately bridging through the N atoms of a C(CN)₂ moiety too. The compounds are characterized by ¹³C NMR, ³¹P NMR and IR spectroscopy. The crystal structure of [AgX(PPh₃)₃] is presented and the structural parameters of the anion in this complex and in [CuX(PPh₃)₂]₂ [X = NCC{C(CN)₂}₂] are compared.     

Synthese und reaktivität von dienylmetall-verbindungen XXVIII. Über kationen des typs [C5H5Fe(CO)L(EME2)]+ (E = S,Se, Te)

The chiral cations, [CpFe(CO)(EMe₂)L]⁺, are obtained both by reaction of [CpFe(CO)(EMe₂)₂]⁺ with the ligands (L) by heating, and by irradiation of the cations [C₅H₅Fe(CO)₂EMe₂]⁺ in the presence of L (E = S, Se, Te; L = PR₃, AsR₃, SbR₃). The inversion about the chalcogen atom is investigated by DNMR spectrocopy. Compounds of the type [C₅H₅Fe(TeMe₂)L₂]⁺] are formed by irradiation of [C₅H₅Fe(CO)₂(TeMe₂)]⁺ and the ligands (L₂ = 2 PR₃, R = CH₃, OCH₃, OC₆H₅; L₂ = R₂P(CH₂)_nPR₂, R = C₆H₅, n = 1,2,3). ⁷⁷Se and ¹²⁵Te NMR data vary according to the donor properties of the ligand L in the complexes.     

Reactions of [WI2(CO)(NCMe)(η2-RC2R)2] (R = Me or Ph) with carbon monoxide to give either [WI2(CO)2(η2-MeC2Me)2] or [W(-I) I(CO) (η2-PhC2Ph)2]2. Crystal structure of [WI2(CO) 2( η2-MeC2Me)2]

The complexes [WI₂(CO)(NCMe)(η2)-RC₂R)₂] (R = Me and Ph) react in CH₂Cl₂ with an excess of carbon monoxide to give initially the acetonitrile substituted products [WI₂(CO)₂(η²-RC₂R) ₂]. For R= Me, the complex [WI₂(CO)₂(η²- MeC₂Me)₂] (1) was isolated and its structure determined by X-ray crystallography. However, for R = Ph, dimerisation occurs to give the iodide-bridged compound [W(μ-I)I(CO)(η²-PhC₂Ph)₂]₂ (2) with loss of carbon monoxide. These reactions are reversible as 1 and 2 react with acetonitrile to give [WI₂(CO)(NCMe)(η²-RC₂R)₂]. The ¹³C NMR spectra of I and 2 indicate that the two alkyne ligands donate a total of six electrons to the tungsten in these complexes.     

Übergangsmetallkomplexe mit Schwefelliganden: XXXIV. [Fe11(CO)2]-Fragmente als Templatzentren und Schutzgruppen: Synthese makrozyklischer Thioether und Monoalkylierung von Dithiolen; Röntgenstrukturanalyse von Dibenzo-18-krone-S6, einem planaren “Kronen”-thioether

Using metal carbonyl fragments as templates, the directed, bridging alkylation of ligating dithiolates yields macrocyclic polythioethers. Treatment of cis-[Fe(CO)₂-(S₂C₆H₄)₂]²⁻ (1) with S(C₂H₄Br)₂, in THF at room temperature, gives [Fe(CO)-(dpttd)] (2) (dpttd²⁻ = 2,3,11,12-dibenzo-1,4,7,10,13-pentathiatridecane(2−)), which is alkylated by yet another S(C₂H₄Br)₂ under reflux to give dibenzo-18-crown-S6 (3) in 68% yield after hydrolysis and workup. Alkylation of [Fe(CO)₂dttd] (dttd² = 2,3,8,9-dibenzo-1,4,7,10-tetrathiadecane(2−)) by S(C₂H₄Br)₂ in THF under reflux gives analogously dibenzo-15-crown-S5 (4) in 20% yield. 4 is also obtained by alkylation of 2 with 1,2-C₂H₄Br₂, but in lower yield. Since each C₆H₄S₂²⁻ ligand in 1 is alkylated only once at room temperature the Fe(CO)₂ fragment acts as a protecting group for one thiolate function and permits the monoalkylation of o-benzenedithiol, a reaction which is not possible by conventional methods; with PhCH₂Br and CH₃Br the corresponding alkylthiobenzenethiols were obtained. An X-ray diffraction study of 3 shows it to have an unprecedented conformation viz. in the centrosymmetric molecule all six sulfur atoms and the C₂ (ethane) bridges form a plane (maximum deviation ± 8 pm) on which the benzo units stand nearly upright (83°). All sulfur atoms are exo and four of the twelve CS bonds show anti configuration. A comparison of the structures of 3 and the analogous oxo compound dibenzo-18-crown-6 are described.     

Übergangsmetall-substituierte acylphosphane und phosphaalkene: XI. Phosphaalkenyl-, disilylphosphido- und diacylphosphidokomplexe des dicarbonylpentamethylcyclopentadienylosmium. Zur kenntnis von [(η5-C5Me5)Os(CO)2]2

The reaction of Os₃(CO)₁₂ with C₅Me₅H in boiling decalin gives the complexes (η⁵-C₅Me₅)(CO)₂OsH and [(η⁵-C₅Me₅)(CO)₂Os]₂. Both compounds were converted into (η⁵-C₅Me₅)(CO)₂OsP(SiMe₃)₂ (III) via the intermediate form (η⁵-C₅-Me₅)(CO)₂OsBr. Complex III was treated with ArC(O)Cl (Ar = Ph, 2,4,6-Me₃C₆H₂) to give mixtures of the phosphaalkenyl complexes (η⁵-C₅Me₅)(CO)₂OsPC(OSiMe₃)(Ar) (IVa, b) and the diacylphosphido complexes (η⁵-C₅Me₅)(CO)₂-OsP[C(O)Ar]₂ (Va, b). Pivaloyl chloride underwent reaction with III to give complex Vc as the only product. The synthesis of the complexes IVa, b includes an E/Z isomerization process.     

Übergangsmetall-heteroallen-komplexe XVII .Reaktionen des aza-allyl-komplexes (ketenimin)Fe2(CO)6 mit phosphanen

The aza-allyl complex (ketene imine)Fe₂(CO)₆ (3a) reacts with phosphanes PR₃ to give substitution products of the type (ketene imine)Fe₂(CO)₅PR₃ (4a,b). In addition, the phosphane PMe₃ yields a ferrole complex (5). Phosphites react with complex 3a to form mono- and di-substitution products (ketene imine)- Fe₂(CO)₅P(OR)₃ (4c,d) and (ketene imine)Fe₂(CO)₄(P(OR)₃)₂ (6). Diphosphanes yield substituted complexes of type (ketene imine)Fe₂(CO)₄(μ-Ph₂P ^⌢ PPh₂) (7). The structures of (ketene imine)Fe₂(CO)₅PMe₃ (4a), the ferrole complex 5, and (ketene imine)Fe₂(CO)₄(ν-Ph₂PCH₂CH₂PPh₂) (7b) were determined by X-ray analysis.     

Synthese von Germanium(I)‐bromid. Ein erster Schritt zu neuen Clusterverbindungen des Germaniums?

Synthesis of Germanium(I) Bromide. A First Step towards New Gemanium Cluster Compounds? Thermodynamic data for gaseous GeBr, derived from quantum chemical (DFT)‐calculations show that this monohalide should be formed at 1550 °C as a product of the reaction of elemental germanium with HBr at 1×10^—2 mbar. Herein the design of an apparatus is described in which GeBr can be synthesized under these conditions and cocondensed with toluene at —196 °C. Using this technique 3 g of a dark red X‐ray amorphous solid could be prepared over a period of 3 hours and was identified to be GeBr. It is shown to undergo disproportionation at 90 °C to give elemental germanium and germanium tetrabromide.