Synthesis and Reactivity of Mono‐, Di‐, and, Triiron Selenocarboxylate Complexes

Treatment of the iron selenide (μ‐Se)[CpFe(CO) 2 ] 2 with one equivalent of 1, 3, 5‐C 6 H 3 (COCl) 3 gave the organoiron selenocarboxylate complex CpFe(CO) 2 SeCO‐3, 5‐C 6 H 3 (COCl) 2 ( 1 ), which contains two free acid chloride groups. Complex 1 reacted with amines, thiols, and phenols to produce the corresponding amides CpFe(CO) 2 SeCO‐3, 5‐C 6 H 3 (CONR 2 ) 2 ( 2 ), thioesters CpFe(CO) 2 SeCO‐3, 5‐C 6 H 3 (COSR) 2 ( 3 ), and aromatic esters CpFe(CO) 2 SeCO‐3, 5‐C 6 H 3 (CO 2 Ar) 2 ( 4 ), respectively. Complex 1 was converted into the diacid CpFe(CO) 2 SeCO‐3, 5‐C 6 H 3 (COOH) 2 ( 5 ) or the diamide CpFe(CO) 2 SeCO‐3, 5‐C 6 H 3 (CONH 2 ) 2 ( 6 ) complexes by reactions with NaOH or NaNH 2 , respectively. The bis(seleno)‐1, 3‐(CpFe(CO) 2 SeCO) 2 ‐5‐C 6 H 3 (COCl) ( 7 ) and tris(seleno)‐carboxylate 1, 3, 5‐(CpFe(CO) 2 SeCO) 3 C 6 H 3 ( 8 ) complexes were also prepared by controlled reaction of 1, 3, 5‐C 6 H 3 (COCl) 3 with the iron selenide (μ‐Se)[CpFe(CO) 2 ] 2 . Complexes 1 – 8 were characterized by spectroscopic techniques (IR, 1 H‐NMR) and by elemental analysis as well. The X‐ray structures of CpFe(CO) 2 SeCO‐3, 5‐C 6 H 3 (COCl) 2 ( 1 ) and CpFe(CO) 2 SeCO‐3, 5‐C 6 H 3 (COSCH 2 Ph) 2 ( 3b ) were determined.