| 16220561 |
van der Vlugt JI, Rauchfuss TB, Wilson SR: Electron-rich diferrous-phosphane-thiolates relevant to Fe-only hydrogenase: is cyanide "nature's trimethylphosphane"?. Chemistry. 2005 Dec 16;12(1):90-8.
The two-step one-pot oxidative decarbonylation of [Fe2 (S2C2H4)(CO) 4 (PMe3) 2] (1) with [FeCp2] PF6, followed by addition of phosphane ligands, led to a series of diferrous dithiolato carbonyls 2-6, containing three or four phosphane ligands. In situ measurements indicate efficient formation of 1 (2+) as the initial intermediate of the oxidation of 1, even when a deficiency of the oxidant was employed. Subsequent addition of PR3 gave rise to [Fe2 (S2C2H4)(mu-CO)(CO) 3 (PMe3) 3] 2+ (2) and [Fe2 (S2C2H4)(mu-CO)(CO) 2 (PMe3) 2 (PR3) 2] 2+ (R = Me 3, OMe 4) as principal products. One terminal CO ligand in these complexes was readily substituted by MeCN, and [Fe2 (S2C2H4)(mu-CO)(CO) 2 (PMe3) 3 (MeCN)] 2+ (5) and [Fe2 (S2C2H4)(mu-CO)(CO)(PMe3) 4 (MeCN)] 2+ (6) were fully characterized. Relevant to the H (red) state of the active site of Fe-only hydrogenases, the unsymmetrical derivatives 5 and 6 feature a semibridging CO ligand trans to a labile coordination site. |
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