Carbonylmetall-Komplexe des Arsinoschwefeldiimid-Achtrings tBuAs(NSN) 2As tBu

Abstract

The eight-membered heterocycle tBuAs(NSN) 2As tBu ( 4), which possesses a boat-like structure, can be incorporated into carbonylmetal complexes either as a monodentate or as a bidentate chelating ligand. The metal fragment is coordinated to the top of the boat-shaped ring system. The reactions of 4 with 16-electron complex fragments ML n(THF) (generated photolytically in THF solution) lead to 1 : 1 adducts of the type ML n( tBuAs(NSN) 2As tBu) where ML n = Cr(CO) 5 ( 5), W(CO) 5 ( 6), CpMn(CO) 2 ( 7) and CpRe(CO) 2 ( 8); attempts to attach a second complex fragment ML n to form a 2 : 1 adduct were unsuccessful. Chelate complexes of the type M(CO) 4 tBuAS(NSN) 2As tBu) (M = Cr ( 10); Mo ( 11), W ( 12)) can be obtained from the reactions of 4 with the norbornadiene compounds M(CO) 4(nor-C 7H 8), while Ni(CO) 2( tBuAs(NSN) 2As tBu) ( 13) is accessible starting from Ni(CO) 4. The complexes 5 and 6 are thermally and photochemically decarbonylated in solution to give the chelate complexes 10 and 12, respectively. The IR, NMR and mass spectra of the new complexes are described.