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• W2054162005 abstract "The dinuclear cobalt complex [(η5-C5Me5)Co(η-(CO)]2 (Me  CH3; 1) adds, when treated with the diazoalkanes 2a–2n, under mild reaction conditions (−80… + 25°C), (CRR′) of different structures to the metal-metal double bond. The novel η-alkylidene complexes 3c–3l, 4a,b,e,n and 5m are formed in mostly quantitative yields following elimination of nitrogen. The triply bridged derivatives 3 are generally more stable than in the series of the analogous rhodium compounds described earlier; usually they form at room temperature the isolated final products. Consecutive structural isomerization and/or decarbonylation yield the secondary products of type 4 and 5. The η-alkylidene complexes 5 open the hitherto best and most straightforward method for the stepwise construction of multiply alkylidene-bridged organometallics: for example, this bis(μ-alkylidene) derivatives 6 and 7 are quantitatively formed when the precursors 5a and 5c, respectively, are treated with diazomethane or diazoethane. The first phosphorylmethylene complex 4n has been obtained by reaction of the cobalt complex 1 with the argentio diazohydrocarbon 2n via elimination of dinitrogen and hydrolysis. The μ-methylene complex (μ-CH2)[(η5-C5Me5)Co(CO)]2 occurs as a mixture of the singly- and the triply-bridged isomers 4a and 3a, both in the solid state and in solution (IR evidence). According to a single-crystal X-ray analysis, trans-oriented sets of equivalent ligands (CO/CO) and C5Me5/C5Me5) are present in the molecule. The dicobaltacyclopropane geometry is characterized by a nearly equilateral Co(1),C,Co(2) triangle having the following bond parameters: d(COC) 190.7(10) and 194.3(8) pm, d(CoCo) 250.2(2) pm (crystal data for 4a: monoclinic, C52h-P21/c; a 966.9(4), b 1688.2(7), c 1419.9(6) pm, β 109.86(3)°; Z  4). Der zweikernige Cobalt-Komplex [(η5-C5Me5)Co(μ-CO)]2 (Me  CH3; 1) addiert unter milden Reaktionsbedingungen (−80… + 25°C) Carbene (CRR′) unterschiedlichster Konstitution an seine Metall—Metall-Doppelbindung, wenn er mit den Diazoalkanen 2a–2n behandelt wird. Unter racher N2-Eliminierung bilden sich dabei die neuen μ-Alkyliden-Komplexe 3c–31, 4a,b,e,n sowie 5m in meist quantitativer Ausbeute. Die dreifach verbrücketen Derivate 3 sind durchwegs beständiger als in der Serie der früher beschriebenen analogen Rhodium-Verbindungen und stellen in der Regel die bei Raumtemperatur isolierbaren Endprodukte dar. Konsekutive Konstitutionsisomerisierung und/oder Decarbonylierung führen zu den Folgeprodukten 4 bzw. 5. Die μ-Alkyliden-Komplexe 5 eröffnen den bisher besten und übersichtlichesten Weg zum stufenweisen Aufbau von mehrfach alkylidenüberbrückten Organometall-Verbindungen: So entstehen die Bis(μ-alkyliden) Derivate 6 und 7 quantitativ, wenn die Vorstufen 5a bzw. 5c mit Diazomethan oder Diazoethan versetzt werden. Durch Umsetzung des Argentiodiazoalkans 2n mit dem Cobalt-Komplex 1 bildet sich nach N2-Eliminierung und Hydrolyse der erste Phosphorylmethylen-Komplex 4n. Der im festen Zustand wie auch in Lösung als Gleichgewicht zwischen den einfach und dreifach verbrücketen Konstitutionsisomeren 4a bzw. 3a vorliegende Methylen-Komplex (μ-CH2[(η5C5Me5)Co(CO)]2 besitzt nach Ausweis einer Einkristall-Röntgenstrukturanalyse trans-ständige Sätze äquivalenter Liganden (CO/CO bzw. C5Me5/C5Me5). Die Dicobaltacyclopropan-Struktur wird durch ein nahezu gleirchseitiges Co(1), C, Co(2)-Dreieck mit d(CoC) 190.7(10) bzw. 194.3(8) pm und d(CoCo) 250.2(2) pm beschrieben (Kristalldaten von 4a: monoklin C52h-P21/c; a 966.9(4), b 1688.2(7), c 1419.9(6) pm, β 109.86(3)°; Z  4)." @default.
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• W2054162005 date "1983-11-01" @default.
• W2054162005 modified "2023-09-23" @default.
• W2054162005 title "Übergangsmetall—methylen-komplexe IL. Alkyliden-cobalt-komplexe:synthese, konstitution, struktur und folgereaktionen" @default.
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• W2054162005 doi "https://doi.org/10.1016/0022-328x(83)89510-2" @default.
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