Result8As previously shown, it is possible to interconvert under very mild conditions the vin ylketene-and vinylcarbene-Fe(CO), complexes 2 and 3 obtained by the reaction of FedCOk with the dimer 1 of diphenylcyclopropene. They thus represent a model system of the carbonylation reaction of a carbene complex. Investigating further the reactivity of complex 3 we studied l;eactions with different phosphanes (PR,, PR,R) and phosphites P(0Rh. Normally displacement of CO and formation of metal-substituted ketene complexes OcCuT. In the case of R = Ph another carbeneketene pair 4a/5a was found to react with CO reversibly, similar to 2 and 3. 3 adds also CH2 to form a (b~tadiene)Fe(CO)~ complex (7). (C5H& Co(CO), also causes ring opening in 1 to yield a vinylketene compound 9 with the CpCo(CO), moiety. The crystal structures of 9 and of three Fe complexes (44% 5a) have been determined.
Praparative Ergebnisse
Eisen-VerbindungenIn Fortfuhrung dieser Arbeiten erfolgten weitere Untersuchungen am Carben-Komplex 3 zunachst mit dem Ziel, dessen Reaktionsfahigkeit gegeniiber Phosphanen und Phosphiten (L) zu priifen. Schema 1 gibt einen Oberblick uber die durchgefuhrten Reaktionen und die dabei erhaltenen Ergebnisse. In allen Fallen erfolgt Addition des Liganden L an das Metall unter Verdrangung einer CO-Gruppe, welche in die Chem.
Bei der Umsetzung von 1,2,3-Triphenylcyclopropenylium-brornid rnit Natrium-tricarbonylnitrosylferrat( -I) in Methanol erhielt Coffey 1962l) in kleinen Ausbeuten eine rotbraune Verbindung. Hierfiir wurden Struktur 1 den Vorzug erhielt.Eine Kurzmitteilung uber eine erneute Untersuchung'' dieser Reaktion veranlal3t uns, unsere eigenen Ergebnisse mitzuteilen.Bei der Umsetzung von [C3Ph3]C1 mit Na [Fe(CO),NO] in THF (20°C) fanden wir vier Produkte (2a, 3, 4, 5), die sich chromatographisch gut trennen liel3en.Die Verbindung 3 ist nach ihren physikalischen und IR-spektroskopischen Daten identisch mit der Coffeyschen Verbindung und konnte von uns u. a. durch eine Ront-0
265ChemInform Abstract Similarly to the interconversion of (III) and (IV), which thus represent a model system for the carbonylation reaction of a carbene complex, the carbene/ketene pair (VI) and (VIIa) is also found to react with CO reversibly. Phosphines other than PPh3 react with (IV) with displacement of CO and formation of the ketene complexes (VIIb)-(VIIe) as confirmed by X-ray structure analysis of (VIIc) (P21/a, Z=4) and (VIId) (P1, Z=2). The structure of (VI) (P1, Z=2) is also determined. (IV) also adds CH2 from diazomethane (VIII) to form the complex (IX). Ring opening in (I) is caused by the Co-complex (X) as well. The vinylketene compound (XI) is characterized by an X-ray structure analysis (C2/c, Z=4).
Die Umsetzung des Cyclopropenyliumchlorids (I) mit dem Ferrat (H) liefert die Titelverbindungen (III) und (IV) neben kleinen Mengen an 2,3‐Diphenyl‐1‐indenon (l.2%) und 1,2,3‐Triphenyleyclopropan (2.5%).
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