Methylmethoxycarben-pentacarbonyl-chrom(0) (2) bildet mit Isonitrilen thermisch stabile, lichtempfindliche Addukte der Zusammensetzung (CO)5CrC(OCH3)CH3.CNR. Fur diese Komplexe wird eine Aziridinyliden-(CO)5Cr-Struktur diskutiert. (CO)5CrC(OCH3)CH3.CNC6H11 (3) geht in Anwesenheit wasriger Sauren unter Methanolabspaltung augenblicklich in (CO)5CrC(COCH3)NHC6H11 (4) uber. Bei Einwirkung von Benzoylperoxid entsteht quantitativ (CO)5CrC[C(CH2)OCH3]NHC6H11 (5), welches unter Saureeinflus zu 4 verseift wird. Methanol bildet ein stabiles Addukt (CO)5CrC[C(OCH3)2CH3] NHC6H11, aus dem mit wasriger Saure ebenfalls 4 erhalten wird. Bei der thermischen Zersetzung von 4 konnte massenspektrometrisch (CO)5CrCNC6H11 nachgewiesen werden. Eigenschaften und Spektren der Verbindungen werden diskutiert.

Übergangsmetall-Carben-Komplexe, IV. Addition von Isonitrilen an Methylmethoxycarben-pentacarbonyl-chrom(0)

Über π-Allyl-Komplexe des Molybdäns II. Die bildung von π-Allyldicarbonylmolybdän-Komplexen aus Molybdän-hexacarbonyl und seinen Derivaten

Allyldicyclopentadienyltitanium(III) and (DI)methylallyl homologues

A new route to π-allyl complexes of molybdenum and tungsten☆

Publisher Summary This chapter discusses coordinately bonded derivatives In the years following World War II, the increasingly large body of experimental data inconsistent with widely held beliefs led to a reassessment of the mechanism of bonding in certain transition metal complexes Common characteristics in complexes exhibiting anomalous behavior are the availability of filled metallic d orbitals and of vacant ligand orbitals with which they could interact The accepted bonding mechanism may be exemplified by consideration of bonding in the octahedral metal carbonyls, for example, Cr(CO)6 The chapter discusses anionic derivatives The anionic derivatives of the group VIB metal carbonyls may be classified (a) Carbonyl metallate ions M(CO)52–, M2(CO)I02–, M3(CO)142–, and possibly higher homologs in which the metal atoms are joined by metal-metal bonds; (b) complex products of the base reactions of the hexacarbonyls, many of which are polynuclear and contain hydroxo or other bridging groups, some of which can be precipitated as the hydrides with strong acids; and (c) Mixed complexes of the zerovalent metal carbonyls and anionic substituents The chapter reviews the π-Arene derivatives of the group VIB metal carbonyls

A.N. Stear

Papers

Some allyl, alkyl and olefin complexes of tungsten