TY - JOUR
T1 - Electron-rich diferrous-phosphane-thiolates relevant to Fe-only hydrogenase
T2 - Is cyanide "nature's trimethylphosphane"?
AU - Van Der Vlugt, Jarl Ivar
AU - Rauchfuss, Thomas B.
AU - Wilson, Scott R.
PY - 2005/12/16
Y1 - 2005/12/16
N2 - The two-step one-pot oxidative decarhonylation of [Fe2-(S 2CH4)(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 12+ 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)(μ-CO) (CO)3(PMe3)3]2+ (2) and [Fe 2-(S2C2H4)(μ-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(S 4C2H4)(μ-CO)(CO)2-(PMe 3)3(MeCN)]2+ (5) and [Fe2-(S 2C2H4)(μ-CO)(CO)(PMe3) 4(MeCN)]2+ (6) were fully characterized. Relevant to the Hrcd 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.
AB - The two-step one-pot oxidative decarhonylation of [Fe2-(S 2CH4)(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 12+ 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)(μ-CO) (CO)3(PMe3)3]2+ (2) and [Fe 2-(S2C2H4)(μ-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(S 4C2H4)(μ-CO)(CO)2-(PMe 3)3(MeCN)]2+ (5) and [Fe2-(S 2C2H4)(μ-CO)(CO)(PMe3) 4(MeCN)]2+ (6) were fully characterized. Relevant to the Hrcd 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.
KW - Hydrogenases
KW - Iron
KW - Phosphanes
KW - Thiolates
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U2 - 10.1002/chem.200500752
DO - 10.1002/chem.200500752
M3 - Article
C2 - 16220561
AN - SCOPUS:29344472529
SN - 0947-6539
VL - 12
SP - 90
EP - 98
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 1
ER -