Übergangsmetall-Carben-Komplexe, LIV. Synthese von übergangsmetall-carbonyl-ylid-Komplexen aus übergangsmetall-carbonyl-carben-Komplexen (original) (raw)

Übergangsmetall-Methylen-Komplexe, LI [1]. Carbocyclische Carbene, Carben-Brücken, kleine Kohlenwasserstoff-Liganden und Metallacyclen: Beispiele einer umfassenden Synthesekonzeption / Transition Metal Methylene Complexes, LI [1]. Carbocyclic Carbenes, Carbene Bridges, Small Hydrocarbon Ligands, ...

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).

Übergangsmetallkomplexe mit Schwefelliganden, LXXX. Synthese, Struktur, Oxotransfer- und redoxgekoppelte Kondensationsreaktionen von Molybdän-Oxo-Komplexen mit dem sterisch anspruchsvollen vierzähnigen Thioether-Thiolat-Liganden 'buS4'2- ('buS4'2- = 1,2-Bis(2-mercapto-3,5-di-t-butylphenylthio)eth...

Zeitschrift für Naturforschung B, 1992

In order to obtain soluble molybdenum sulfur oxo complexes, [Mo(O)2('buS4')] (1) ('buS4'2- = 1,2-bis(2-mercapto-3,5-di-t-butylphenylthio)ethane(2-)) was synthesized by reaction of [Mo(O)2(acac)2] (acac- = acetylacetonate(1-) ) with 'buS4'-Li2. Treatment of 1 with PPh3 yielded [μ-O{Mo(O)('buS4')}2] (2) and OPPh3 in an oxo transfer reaction. [Mo(PMe3)2('buS2')2] (3) ('buS2'2- = 3,5-di-t-butyl-1,2 -benzenedithiolate(2-)) was obtained by twofold desoxygenation of 1 with excess PMe3 via a redox coupled addition elimination reaction. 2 reacts with the oxo group donor DMSO to yield 1 and Me2S. The system 1/2 then catalyses the oxo transfer reaction from DMSO to PPh3 and, therefore, shows properties modelling the co-factor in oxotransferases. In contrast to the parent compound [Mo(O)2('S4')] ('S4'2- = 1,2-bis(2-mercaptophenylthio)ethane(2-)), 1 is reactive towards hydrazine and its derivatives. Reactions with hydrazine and alky...

Metallcarbonyl‐Synthesen, XX. Einfache Methode zur Darstellung von Tc(CO) 3 ‐Komplexen: Synthese und Struktur der neuartigen Technetium(I)‐Clusterverbindung Na[Tc 3 (CO) 9 (OCH 3 ) 4 ] mit Cuban‐Struktur

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.