Abstract
The reactions of the tetrahedral cluster [SeFe 3 (CO) 9 ] 2- with some transition-metal complexes and organic halides were investigated. The mixed-metal cluster [Et 4 N] 2 [SeFe 2 -Ru 3 (CO) 14 ] (1) was obtained from the reaction of [Et 4 N] 2 [SeFe 3 (CO) 9 ] with Ru 3 (CO) 12 in acetone. Further reaction of [Et 4 N] 2 [SeFe 3 (CO) 9 ] with HgI 2 produces the HgI-bridged cluster [Et 4 N][SeFe 3 (CO) 9 (μ-HgI)] (2). While [SeFe 3 (CO) 9 ] 2- reacts with CHPhCl 2 to produce the CHPh-bridged cluster Fe 2 (CO) 6 (μ-SeCHPhSe) (3), treatment with CH 2 I 2 forms the major product Se 2 Fe 2 (CO) 6 (μ-CH 2 ) 2 (4). Complex 1 displays an octahedral metal core with a μ 4 -Se atom and two carbonyl groups bridging the Ru-Ru and Ru-Fe bonds. Cluster 2 consists of a SeFe 3 core with a HgI fragment bridging one Fe-Fe bond, and cluster 3 exhibits a Se 2 Fe 2 butterfly geometry with the wingtip linked by a CHPh moiety. On the other hand, cluster 4 contains a planar Se 2 Fe 2 moiety with two CH 2 groups bridging the two Se-Fe bonds. Complexes 1-4 have been fully structurally characterized by spectroscopic methods and X-ray diffraction analyses. This paper describes the formation of four different types of clusters from the reactions of [SeFe 3 (CO) 9 ] 2- with electrophiles and discusses the role of [SeFe 3 (CO) 9 ] 2- and the incoming electrophiles.