Di-iron aza diphosphido complexes: mimics for the active site of Fe-only hydrogenase, and effects of changing the coordinating atoms of the bridging ligand in [Fe2[mu-(ECH2)2NR](CO)6].
The bis(phosphido)-bridged complex [Fe(2)(mu-PPhH)(2)(CO)(6)] (1) undergoes double deprotonation to give the phosphorus-centered dianionic derivative [Fe(2)(mu-PPh)(2)(CO)(6)](2)(-) (2) which in turn reacts with the tertiary base RN(CH(2)Cl)(2) to give [Fe(2)[(PPhCH(2))(2)NR](CO)(6)] (3) in moderate yield. Treatment of 3 with HBF(4).Et(2)O affords the N-protonated species [Fe(2)[(PPhCH(2))(2)NHR](CO)(6)] BF(4) (4). The structural changes to the heavy atom skeleton of 3 arising from protonation are slight, the most obvious being a ca. 0.03 Alengthening of the N-C bonds.
Das
Pankaj
P
UMR CNRS 6521, Chimie, Electrochimie Moléculaires et Chimie Analytique, Faculté des Sciences, Université de Bretagne Occidentale, 6 Avenue Le Gorgeu, C.S. 93837, 29238 Brest Cedex 3, France.
Capon
Jean-François
JF
Gloaguen
Frédéric
F
Pétillon
François Y
FY
Schollhammer
Philippe
P
Talarmin
Jean
J
Muir
Kenneth W
KW
D001372:Aza Compounds / Q000737:chemistry*; D001665:Binding Sites; D018360:Crystallography, X-Ray; D005296:Ferrous Compounds / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D018716:Molecular Mimicry; D015394:Molecular Structure; D009943:Organophosphorus Compounds / Q000737:chemistry*
D001372:Aza Compounds; D005296:Ferrous Compounds; D007506:Iron-Sulfur Proteins; D009943:Organophosphorus Compounds; C118830:iron hydrogenase; D006864:Hydrogenase