Transformationen von Clustern mit dem (μ3-RP)Fe3(CO)9-Gerüst. Synthese und Reaktionen von ([μ3-RP)Fe3(CO)9]2−

Abstract The clusters (μ 3 -RP)Fe 3 (CO) 10 ( 1 ) or (μ 3 -RP)Fe 3 (CO) 9 (μ 2 -H) 2 ( 2 ) can reversibly be transformed into the cluster anions [(μ 3 -RP)Fe 3 (CO) 9 (μ 2 -H)] − ( 3 ) and [(μ 3 -RP)Fe 3 (CO) 9 ] 2− ( 4 ). The pyrophoric clusters 4 react with the divalent electrophile CH 2 I 2 to give the complexes (μ 3 -η 2 -RP=CH 2 )Fe 3 (CO) 10 ( 5 ), which contain a cluster-stabilized phosphaalkene, RP=CH 2 , as a ligand. With monovalent electrophiles R′X, such as Me 2 SO 4 , compound 4 (R = anisyl), yields, upon protolytic work-up, the complexes (μ 3 -η 3 -R′P-anisyl)Fe 3 (CO) 9 (μ 2 -H) ( 6 ) in which the phosphorus-bound aryl residue of the μ 2 -bridging phosphide ligand (R′P-anisyl) forms an η 2 -coordination to the third iron atom of the cluster. The η 2 -coordination of the aryl substituent may be reversibly released by two-electron ligands L under formation of (μ 2 -R′P-anisyl)(μ 2 -H)Fe 3 (CO) 9 L ( 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.