Ligandeneffekte bei der Synthese der Komplexe ClRh()(PO), )2> und )>

Article abstract of DOI:10.1016/0022-328X(93)80479-U

The behaviour of rhodium(I) complexes <(μ-Cl)Rh(COE)2>2 (1, COE = cyclooctene) and <(μ-Cl)Rh(COD)>2 (6, COD = 1,5-cyclooctadiene) towards a series of ether-phosphines of the type R2PCH2CH2OCH3 (R = ^tBu (2a), ⁱPr (2b), Cy (2c), Ph (2d)) was examined.Complex 1 reacts with 2b,c to give pure RhCl(<*>)(P<*>O) (4b,c, <*>: η²-bonded O,P ligand; P<*>O: η¹-bonded O,P ligand).In contrast, treatment of 1 with 2d predominantly yields <(μ-Cl)Rh(P<*>O)2>2 (3d), which may be photochemically converted into 4d.In the presence of NaBPh4, the reaction of 1 with 2b,cresults in the formation of the bis(chelate) complex cis-)2> (5b,c). 5d, however, is only accessible by Cl^- abstraction from 4d.Treatment of 6 with 2a-c and NaBPh4 affords <(COD)Rh(<*>)> (7a-c), whereas 2d gives <(COD)Rh(P<*>O)2> (8d).