TRANSFORMATIONEN VON CLUSTERN MIT DEM (μ3-RP)Fe3(CO)9-GERUEST. SYNTHESE UND REAKTIONEN VON 3-RP)Fe3(CO)9>2-

Article abstract of DOI:10.1016/S0022-328X(00)99555-X

The clusters (μ₃-RP)Fe3(CO)10 (1) or (μ₃-RP)Fe3(CO)9(μ₂-H)2 (2) can reversibly be transformed into the cluster anions <(μ₃-RP)Fe3(CO)9(μ₂-H)>^- (3) and <(μ₃-RP)Fe3(CO)9>^2- (4).The pyrophoric clusters 4 react with the divalent electrophile CH2I2 to give the complexes (μ₃-η²-RP=CH2)Fe3(CO)10 (5), which contain a cluster-stabilized phosphaalkene, RP=CH2, as a ligand.With monovalent electrophiles R'X, such as Me2SO4, compound 4 (R = anisyl), yields, upon protolytic work-up, the complexes (μ₃-η³-R'P-anisyl)Fe3(CO)9(μ₂-H) (6) in which the phosphorus-bound aryl residue of the μ₂-bridging phosphide ligand (R'P-anisyl) forms an η²-coordination to the third iron atom of the cluster.The η²-coordination of the aryl substituent may be reversibly released by two-electron ligands L under formation of (μ₂-R'P-anisyl)(μ₂-H)Fe3(CO)9L (7).In addition, the transformation sequence of 5 into 6 is accomplished by an H^-, H⁺ addition sequence.The experiments are documented by analytic and spectroscopic data as well as by X-ray analyses.