Metallorganische Synthesen mit freien Cyclopentadienyl-Radikalen, I. Zweikernige Carbonylnickel-Komplexe mit mehrfach alkylierten Cyclopentadienyl-Liganden / Metalorganic Syntheses with Free Cyclopentadienyl Radicals, I. Dinuclear Carbonyl Nickel Complexes with Alkylated Cyclopentadienyl Ligands (original) (raw)
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Zeitschrift für Naturforschung B, 1987
Reaction of Cp2Ti(CO)2, Cp=h5-C5H5, with the 1,2-diazenes ROCN = NCOR (R = EtO (1a), tert-BuO (1b), p-MeC6H4O (1c), p-MeC6H4 (1d)) in the molar ratio of 1:1 yiclds five- membered metallacycles 2 by formal 1,4-addition of 1 to the Cp2Ti fragment. When a two-fold excess of Cp2Ti(CO)2 is employed, the initially formed 2 reacts further by N = N-cleavage to give Cp2Ti(NCO)(OR), Cp2Ti(NCO)2 and Cp2Ti(OR)2 resp., in the case of 1a-1c. The bis(p-methyl- benzoyI)diazene (1d) does not afford analogous cleavage products. Dimethyl- and pentamethy- lenediazirine also react by cleavage of the N = N-bond to afford Cp2Ti(NCO)(N=CR2).
Zeitschrift für Naturforschung B, 1983
Carbene Transfer, Metal-Metal Multiple Bonds Carbene transfer from aliphatic diazoalkanes upon coordinatively unsaturated metal centers is a general synthetic concept that provides straightforward routes into organometallic hydrocarbon chemistry. A comparison focussing on several key reactions of general applicability demonstrates that mononuclear organometal substrates add carbenes that may act as bridging ligands (e.g., compound 6) if they arise from u>,co'-bisdiazoalkanes. By way of contrast, metal-metal double bonds cleanly form dimetallacyclopropane-type derivatives under very mild conditions (7-9). The broadest variety of structures is finally encountered with metal-metal triply bonded precursors such as the molybdenum compounds 3: here, the initial diazoalkane adducts are subject to further rearrangement processes commonly leading to metal-metal single bonds (11) or causing irreversible cleavage of the dinuclear metal systems (10).
Chemische Berichte, 1991
Technetium complexes / Isocarbonyl ligand Metal Carbonyl Syntheses, XX 'I.-Simple Method for the Preparation of T C (C O)~ Complexes: Synthesis, Structures, and Reactivity of the Novel Cubane-Type Cluster N~[ T C~(C O)~(O C H & ] Carbonyltechnetium complexes of type LTC(CO)~ are acces-conducted in methanol. Under carbon monoxide pressure, 2 sible along a simple route from N~[ T C~(C O)~(O C H~)~] (2) which yields the binary metal carbonyl T c~(C O)~~ (3), pentamethylrepresents a novel alkoxy complex of cubane-type geometry cyclopentadiene gives the halfsandwich complex (11,-(single-crystal X-ray diffraction study). 2 is a n isolable product C,Me,)Tc(C0)3 (4), and with benzene/hydrochloric acid the of the incomplete carbonylation of sodium pertechnetate (1) ionic complex [(q6-C6H6)T~(C0)3]C1 (5) is formed.
Monatshefte f�r Chemie Chemical Monthly, 1996
This synthetic and structural work describes a series of half-sandwich cyclopentadienylruthenium(II) complexes containing the diphosphazane ligands [(C6H5)2P]2NR (R = H:Hdppa, la; R = CH 3 : dppma, lh; R = C2H s :@pea, lc; R = Li: Lidppa, ld). Treatment of la, d with CpRnC1 (PPh3) 2 (Cp = t/s-CsHs, Ph = C6Hs, 2) in a molar ratio of 1:1 in boiling aromatic hydrocarbons affords the neutral complexes CpRuCl(Hdppa) (3) and CpRu(dppa)PPh 3 (6). The ionic complexes [CpRu(Ph2P-NR-PPh2)PPh3)C1 (R = CH3: 4a; R = C2Hs: 4h) are formed by the reaction of lb, e with 2. One pot reactions of la c with 2 in the presence of NH4PF 6 in boiling CH3OH give only the ionic compounds [-CpRu(Ph2P-NR-PPh2)(PPh3)]PF 6 (R = H, CH3, C2H5; 5a-c). The sulfur dioxide and hydride complexes [CpRu(Hdppa)ql-SO2]C1 (7) and CpRu(H)Hdppa (8) are obtained by the interaction of 3 with SO 2 or NaOCH 3. All compounds are characterized as far as possible by IR, Raman, 31P{1H} NMR, 1H NMR, 13C{1H} NMR, FD mass spectra, and their conductivity in CH2C12 solution. The X-ray crystal structures of 3 and 5a reveal that the P(1)-N(1)-P(2) angle of the coordinated ligand la in both complexes is reduced to about 100 ° in comparison to free uncoordinated la (119°). This small angle leads to a short P(1)-P(2) bond distance of 259.4pm in 3 and 2543 pm in 5a. The molecules of 3 are connected by intermolecular (NH... C1) hydrogen bridging bonds forming chains along the z axis of the unit cell. The crystals of 5a contain two independent pairs of ions in the unit cell (Z = 8). In 5a no hydrogen bonds exist between the NH-groups and the PF 6 anions.
Monatshefte fuer Chemie/Chemical Monthly, 1998
Summary. The metalation of bis(diphenylphosphanyl)amine, HN(PPh2)2 (5), with RbOtBu in the presence of N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDTA (3)) in toluene surprisingly affords the nearly PMDTA free RbN(PPh2)2 (6a). Recrystallization of 6a from tetrahydrofuran (THF) yields RbN(PPh2)2ċ0.5 THF (6b). Compounds 6a, b crystallize in thin needles; however, these are not suitable for X-ray structure analyses. The reactions of 5 with MOtBu (M=Rb, Cs) in