Unexpected Synthesis of Tetrahedral Fe/S Clusters via Highly Reactive Butterfly Intermediates (μ-HS)2Fe2(CO)5[RP(CH2OH)2]

Reactions of butterfly complex (mu-HS)(2)Fe-2(CO)(6) (1) with RP(CH2OH)(2) under N-2 followed by TLC separation in air gave the unexpected tetrahedral complexes (mu-S-2)Fe-2(CO)(5)[RP(CH2OH)(2)] (4a, R = Ph; 4b, eta(5)-C5H4CH2FeCp). While the suggested pathway for production of 4a,b was proved by isolation and characterization of the very air-sensitive intermediate (mu-HS)(2)Fe-2(CO)(5)[PhP(CH2OH)(2)] (M-1), the in situ reaction of M-1 with I(CH2)(3)I and Et3N allowed us to obtain model complex (mu-PDT)Fe-2(CO)(5)[PhP(CH2OH)(2)] (5).