Syntheses of new Fe/Se clusters via the reactions of PhC(Se)NHCH2Ph, Et3N and Fe3(CO)12 with electrophiles

Abstract The selenoamide-based route to synthesize new Fe/Se cluster complexes has been investigated. The three-component reaction of PhC( Se)NHCH 2 Ph, Et 3 N and Fe 3 (CO) 12 affords the [Et 3 NH] + salt of the [(μ-PhC NCH 2 Ph)Fe 2 (CO) 6 (μ-Se)] − cluster anion. The Se-centered cluster anion reacts with PhCH 2 Br to give (μ-k 2 C,N-PhC NCH 2 Ph)Fe 2 (CO) 6 (μ-SeCH 2 Ph) ( 1 ). Furthermore, trapping the Se-centered cluster anion with PPh 2 Cl offers (μ-k 2 C,N-PhC NCH 2 Ph)Fe 2 (CO) 6 (μ-k 2 Se,P-SePPh 2 ) ( 2 ). Treating the Se-centered cluster anion with CF 3 CO 2 H leads to [(μ-k 2 C,N-PhC NCH 2 Ph)Fe 2 (CO) 6 ] 2 (μ 4 -Se 2 ) ( 3 ) and [(μ-k 2 C,N-PhC NCH 2 Ph)Fe 2 (CO) 6 (μ 4 -Se)] 2 Fe 2 (CO) 6 ( 4 ). More interestingly, reacting with Fe 3 (CO) 12 forms the [Et 3 NH] + salt of the [(μ-PhC NCH 2 Ph)Fe 2 (CO) 6 (μ 4 -Se)Fe 2 (CO) 6 (μ-CO)] − cluster anion. Treating the μ-CO-containing cluster anion with (1,2-O 2 C 6 H 4 )PCl produces (μ-k 2 C,N-PhC NCH 2 Ph)Fe 2 (CO) 6 (μ 4 -Se)Fe 2 (CO) 6 (μ-(1,2-O 2 C 6 H 4 )P) ( 5 ). All the new cluster complexes have been unequivocally determined by X-ray crystallography and completely characterized by microanalyses, IR, 1 H NMR, 13 C NMR and 77 Se NMR as well as 31 P NMR for 2 and 5 . Therefore, the reactions of PhC( Se)NHCH 2 Ph, Et 3 N and Fe 3 (CO) 12 , via the [(μ-PhC NCH 2 Ph)Fe 2 (CO) 6 (μ-Se − )] cluster anion, with electrophiles demonstrate an unprecedented route to new Fe/Se cluster complexes.