Derivate des borols: IX. (η5-borol)metall-komplexe von ruthenium,osmium und rhodium

Dehydrogenating complexation of borolenes with carbonyls (Ru₃(CO)₁₂, Os₃(CO)₁₂), Wilkinson's catalyst (RhCl(PPh₃)₃) and related compounds (RuCl₂(PPh₃)₃, RuHCl(PPh₃)₃, OSCl₂(PPh₃)₃), and (η⁶-arene)ruthenium complexes (Ru(η-C₆H₆)(η⁴-C₆H₈), [Ru(η-C₆H₆)Cl₂]₂, [Ru(η-C₆-Me₆)Cl₂]₂) leads to the (η⁵-borole)metal complexes of Ru, Os, and Rh. Inter alia, the preparation of the complexes Ru(CO)₃(η⁵-C₄H₄BF) (R = Ph, OMe, Me), Os(CO)₃L (L = η⁵-C₄H₄BPh), MHClL(PPh₃)₂ (M = Ru, Os), RhClL(PPh₃)₂, and RuL(η-C₆R₆) (R = H, Me) is described. The structures of RuHClL(PPh₃)₂ and RhClL(PPh₃)₂ have been determined by X-ray diffraction analysis.     

Derivate des borols: VII. (η5-borol)rhodium-komplexe und nucleophiler abbau von μ-(η5-1-phenylborol)-bis[(η5-1-phenylborol)rhodium]

Dehydrogenating complexation of borolenes C₄H₆BR (R = Me, Ph) with [Rh(η²-C₂H₄)₂Cl]₂ gives the triple-decked complexes μ-L-(RhL)₂ (III) with L = η⁵-C₄H₄BR. Cyclopentadienide degradation of III gives the uncharged complexes CpRhL (IV) and the water-soluble salts Na[RhL₂] (Na⁺ · V) which are characterized as NMe₄⁺ (R = Me) and Cs⁺ salts (R = Ph). In CD₂Cl₂/CF₃CO₂D the complex CpRh(η⁵-C₄H₄BPh) shows fast exchange at the α-position to the boron at 0°C, thus providing the first evidence of an electrophilic substitution of an (η⁵-borole)metal complex. Protonation of V gives RhHL₂ (VII) as the first (η⁵-borole)metal hydrides. Various neutral nucleophiles effect a valence disproportionation of IIIb (R = Ph) with formation of the compounds [LRhY₃][RhL₂] (VIII) (Y = PMe₃), IX (Y = P(OMe)₃), and X (Y = CNBu^t). Cyanide degradation of IIIb in acetonitrile yields K₂[LRh(CN)₃], characterized as PPh₄⁺ salt (XII). Further degradation in aqueous solution provides the anion [C₄H₄B(CN)Ph]⁻ (XIII) isolated as the [CoCp₂]⁺ salt (XIV). Anion XIII constitutes the first Lewis-base adduct of a simple, i.e. C-unsubstituted borole.     

Derivate des Methylendioxybenzols, 6. Mitt.: Über die Gewinnung und elektrophile Substitutionen des Myristicinsäuremethylesters und seiner Derivate

Zusammenfassung Aus dem Petersiliensamenöl isolierten wir Apiol, Myristicin und Safrol. Durch Ozonisierung wurden die entsprechenden Aldehyde dargestellt, die zur Säure weiteroxydiert und als Ester getrennt werden konnten. Außerdem beschreiben wir die Bildung von Brom-, Nitro- und Aminoderivaten des Myristicinsäuremethylesters.1. Mitt.:F. Dallacker, Ann. Chem.633, 14 (1960); 2. Mitt.:F. Dallacker, ebenda633, 23 (1960); 3.-5. Mitt.:F. Dallacker, K. W. Glombitza undM. Lipp, ebenda, im Druck.     

Structural properties of the trimetallic acetylide complex [{Ru(CO)2(η5C5H5)}3(η1:η1:η2:-CC)]+

The purpose of this Note is the study of the structure and fluxional behavior of the complex [{Ru(CO)₂(η⁵C₅H₅)}₃(η¹:η¹:η²:-CC)]⁺, using density functional methods. The molecular geometry of this complex will be optimized, the transition state (TS) of the fluxional process will be determined and the origin of the energy barrier will be analyzed.     

N-(η5-Cyclopentadienylvanadium)benzenesulfonamide

N-(⁵-Cyclopentadienylvanadium)benzenesulfonamide has been synthesized for the first time by treating benzenesulfonamide orN-(tributylstannyl)benzenesulfonamide with vanadocene.Deceased.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2107–2109, December, 1993.     

Crystal structure of twinned (η5-C5(CH3)4CF3) (η5-C5(CH3)5)Ru

The substituted sandwich complex crystallizes in monoclinic space groupP2₁/m withZ=2. Twinning to the (001) direction with the special conditionc ^*/4a ^* = cos ^* causes systematic superposition of the reciprocal lattices of both domains and results in an apparent unit cell with double volume and the reflection condition (2h)kl, l=2n. The structure solution was obtained with the subset of intensity data for the predominant individuum and converged atR = 0.040,R _w =0.046 for 832 independent observations and 122 variables. The molecules show disorder with respect to the crystallographic mirror plane. The structure is closely related to that of decamethylruthenocene.     

Electron transfer in organometallic clusters: XIV. Crystal and electronic structures of the tricobalt carbon cluster (η5-C5H5)Fe[η5-C5H4-CCo3(CO)9] and the biscarbyne cluster (η5-C5H5)Fe[η5-C5H4CCo3(η5-C5H5)3CH]

The crystal and molecular structures of (η⁵-C₅H₅)Fe[η⁵--C₅H₄CCo₃(CO)₉] (1), Pna2₁, α 17.354, b 11.463, c 11.207 Å Z = 4, R = 0.053, R_w = 0.056 for 939 reflections (I>3σ(I)) at 293 K, and (η⁵-C₅H₅Fe[η⁵--C₅H₄CCo₃(η⁵C₅H₅)₃CH] (2), P2₁/n, a 13.807(9), b 11.254(4), c 13.991(9) Å, β 99.98(5)°, Z = 4, R = 0.033 and R_w = 0.033 for 3051 observed reflections (I>3σ(I)) at 180 K, have been determined by X-ray methods.The results provide a detailed characterisation of related tricobalt-carbon complexes directly bound to ferrocene residues. In 1 the ferrocenyl moiety tops the pyramidal CCo₃ cluster core, while in 2 the CCo₃C core is bipyramidal with a ferrocenyl substituent on one capping carbon atom and a hydrogen atom at the other. In both cases the ferrocenyl group is tilted towards one cobalt atom of the cluster core, a distortion believed to be the consequence of the non-degeneracy of the carbyne p(π) orbitals resulting from a cooperative π-interaction between the clusters and the ferrocenyl substituents.     

Structure and reactivity of substituted di-η5-cyclopentadienyl metal dihalides. Crystal structure of dichlorobis(η5-t-butylcyclopentadienyl)zirconium(IV)

A new approach to the synthesis of t-butylcyclopentadienyl and related anions, via the addition of methyl- or other alkyl-lithium compounds to dimethylfulvene, is reported and details are given for the preparation of (η⁵-t-BuCp)₂ZrCl₂ and (η⁵-t-BuCp)₂TiCl₂. The zirconium compound is orthorhombic, P2₁2₁2, a 13.003(17), b 10.761(10), c 6.703(8) Å. A crystal structure determination (R = 0.037, 980 reflections) shows that the t-butyl groups are directed away from each other on opposite sides of the molecule: this structure appears to be adopted only in molecules in which the substituent groups are too bulky to be accommodated directly above and below the MCl₂ group.     

Untersuchungen über Phenthiazinderivate, 15. Mitt.: Neue Derivate des Phenthiazinyl-(3)-äthanolamins und deren Vorstufen

Zusammenfassung In der Reihe der Phenthiazinyl-(3)-äthanolamine wird die Synthese von neuen Basen beschrieben sowie die von Halogeniden, die für diese und ähnlich gebaute Verbindungen als Ausgangsmaterial dienen können.     

Replacement of terminal and bridging oxo groups by phenylimido groups in (η-C5H5)OMo(μ-O)2OMo(η-C5H5) giving (η-C5H5)(NPh)Mo(μ-NPh)2Mo(NPh)(η-C5H5)

The treatment of (η-C₅H₅)OMo(μ-O)₂MoO(η-C₅H₅) with excess phenylisocyanate at reflux in tetrahydrofuran yields the arylimido-substituted complex (η-C₅H₅)(NPh)Mo(η-NPh)₂Mo(NPh)(η-C₅H₅), which has been characterized by elemental analysis, and mass, IR and ¹H NMR spectra.