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• W2146452607 abstract "In praktisch quantitativen Ausbeuten reagieren die aliphatischen Diazoverbindungen 2a–o im Temperaturbereich -80/+25°C mit dem zweikernigen Carbonylrhodium-Komplex 1 unter N2-Eliminierung und gleichzeitiger Carben-Addition an die RhRh-„Doppelbindung”︁. Der Einfluß der Methylen-Brücken auf die Konstitution der neuen Dimetallacyclopropane 3k,l,n,o, 4a–j, m und 5l bleibt weitgehend auf sterische Effekte beschränkt und spiegelt sich in den Molekülstrukturen der Schlüsselbeispiele 3o und 4g wider. Die teils reversiblen Decarbonylierungs-Reaktionen 3→5 und 4→5 verlaufen nach kinetischen Untersuchungen als Direktprozesse ohne Beteiligung von Zwischenstufen signifikanter Konzentration. Das in den Verbindungen 5 wiederhergestellte charakteristische Strukturelement der reaktiven Vorstufe 1 eröffnet mit der konsekutiven Carben-Addition die Möglichkeit zur gezielten Synthese von Bis(μ-methylen)-Komplexen mit unterschiedlichen CR2-Liganden (z. B. 6). Transition Metal Methylene Complexes, XXVIII. Carbene Addition to Metal Metal Multiple Bonds. Synthesis and Molecular Structures of Novel μ-Methylene Rhodium Complexes Reaction of the aliphatic diazo compounds 2a–o with the dinuclear carbonylrhodium complex 1 in the temperature range -80/+25°C leads to N2-elimination and quantitative carbene addition to the rhodium-rhodium „double bond”︁. The influence of the methylene bridges upon the constitution of the novel dimetallacyclopropane-type compounds 3k,l,n,o, 4a–j, m, and 5l is largely restricted to steric effects which is reflected by the molecular structures of the typical examples 3o and 4g. The decarbonylation reactions 3→5 and 4→5 are in part reversible and, according to kinetic studies, do not involve any intermediate of significant concentration. The structural characteristics of the reactive precursor 1 is reestablished in compounds 5. Consecutive carbene addition to 5 opens a synthetic route to bis(μ-methylene) complexes having structurally different CR2-ligands, e. g. 6." @default.
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• W2146452607 date "1982-03-01" @default.
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• W2146452607 title "Übergangsmetall-Methylen-Komplexe, XXVIII. Carben-Addition an Metall–Metall-Mehrfachbindungen. Synthese und Molekülstrukturen neuer μ-Methylen-Rhodium-Komplexe" @default.
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• W2146452607 doi "https://doi.org/10.1002/cber.19821150306" @default.
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