Synthese, Struktur und Reaktivität labiler Rhodium(I)-Komplexe mit iPr2PC2H4NMe2 und iPr2PC2H4OMe als Phosphanliganden / Synthesis, Structure and Reactivity of Labile Rhodium(I) Complexes Containing iPr2PC2H4NMe2 and iPr2PC2H4OMe as Phosphine Ligands

Abstract

Square-planar rhodium(I) complexes [RhCl(iPr2PC2H4Y)2] (8, 9) containing one chelating and one P-bonded monodentate phosphine ligand are prepared from [RhCl(C8H14)2]2 (7) and the new functionalized phosphines iPr2PC2H4Y (5,6). Reaction of 9 (Y = NMe2) with CO and of 8 (Y = OMe) with CO, C2H4, C2H2, C2Ph2 and HC2Ph leads to opening of the chelate ring and formation of the complexes trans-[RhCl(L)(η1-P–iPr2PC2H4Y)2] (10-15). Treatment of 8 with H2 gives the dihydridorhodium(III) compound [RhH2Cl(iPr2PC2H4OMe)2] (16). The vinylidene complexes trans-[RhCl(=C=CHR)(η1-P– iPr2PC2H4OMe)2] (17, 18) are obtained by thermal or pyridine promoted rearrangement of 13 (L = C2H2) and 15 (L = HC2Ph). 13 and 15 have also been used as starting materials for the synthesis of the cyclopentadienyl alkyne and vinylidene complexes 19-21. The X-ray crystal structure of the parent compound 8 was determined.