The electrophilic tetranuclear complex [(Cp′Mo(µ-S)) 2 (S 2 CH 2 )] 2 (BF 4 ) 2 (1: Cp′ ) C 5 H 5 (1a), C 5 H 4 Me (1b)), in which two dinuclear complexes are joined by a sulfur-sulfur bond, reacts with the electron-rich nitrogen heterocycles pyrroles and indoles at room temperature. The reactions involve heterolytic scission of the disulfide bond by the nucleophiles followed by proton transfer, and the products areThe reactions have been characterized for pyrrole, 1-methylpyrrole, 1,2,5-trimethylpyrrole, and 1-methylindole. The regiochemistry of the reactions depends on pyrrole substituents. Complex 1 also reacts readily with the coordinated pyrrolyl ligand in (PMe 2 Ph) 3 Cl 2 Re(NC 4 H 4 ). The electrophilic substitution occurs on the 3-position of the heterocycle to form [(Cp′Mo) 2 (S 2 CH 2 )(µ-S)(µ-SC 4 H 3 N)ReCl 2 (PMe 2 Ph) 3 ]BF 4 (7). Complex 7 undergoes a further reaction with 1 to give the hydrogen abstraction product [(Cp′Mo) 2 (S 2 CH 2 )(µ-S 2 C 4 H 2 N)ReCl 2 (PMe 2 Ph) 3 ]BF 4 ( 8). An X-ray diffraction study of 8b confirms that the 3-and 4-carbons of the pyrrolyl ligand are coordinated to the µ-sulfido ligands of the molybdenum dimer. The new products suggest that there are a number of ways in which electron-rich heterocycles might interact with a sulfided molybdenum catalyst in the hydrodenitrogenation reactions. Reactions of 1 with other nucleophiles have also been surveyed.
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