TY - JOUR
T1 - Characterization of a borane σ complex of a diiron dithiolate
T2 - Model for an elusive dihydrogen adduct
AU - Lalaoui, Noémie
AU - Woods, Toby
AU - Rauchfuss, Thomas B.
AU - Zampella, Giuseppe
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/6/12
Y1 - 2017/6/12
N2 - The azadithiolate complex Fe2[(SCH2)2NMe](CO)6 reacts with borane to give an initial 1:1 adduct, which spontaneously decarbonylates to give Fe2[(SCH2)2NMeBH3](CO)5. Featuring a Fe-H-B three-center, two-electron interaction, the pentacarbonyl complex is a structural model for H2 complexes invoked in the [FeFe]-hydrogenases. The pentacarbonyl compound is a "σ complex", where a B-H σ bond serves as a ligand for iron. The structure of this σ complex was characterized by variableerature NMR spectroscopy and X-ray crystallography. Complementary to the 1:1 borane adduct is the quaternary ammonium complex [Fe2[(SCH2)2NMe2](CO)6]+, which was also characterized. It represents a kinetically robust analogue of the N-protonated amine cofactor, as indicated by its mild reduction potential.
AB - The azadithiolate complex Fe2[(SCH2)2NMe](CO)6 reacts with borane to give an initial 1:1 adduct, which spontaneously decarbonylates to give Fe2[(SCH2)2NMeBH3](CO)5. Featuring a Fe-H-B three-center, two-electron interaction, the pentacarbonyl complex is a structural model for H2 complexes invoked in the [FeFe]-hydrogenases. The pentacarbonyl compound is a "σ complex", where a B-H σ bond serves as a ligand for iron. The structure of this σ complex was characterized by variableerature NMR spectroscopy and X-ray crystallography. Complementary to the 1:1 borane adduct is the quaternary ammonium complex [Fe2[(SCH2)2NMe2](CO)6]+, which was also characterized. It represents a kinetically robust analogue of the N-protonated amine cofactor, as indicated by its mild reduction potential.
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U2 - 10.1021/acs.organomet.7b00236
DO - 10.1021/acs.organomet.7b00236
M3 - Article
AN - SCOPUS:85020710052
SN - 0276-7333
VL - 36
SP - 2054
EP - 2057
JO - Organometallics
JF - Organometallics
IS - 11
ER -