Lewis vs. Brønsted-basicities of diiron dithiolates: spectroscopic detection of the "rotated structure" and remarkable effects of ethane- vs. propanedithiolate.
The new complexes Fe2(S2CnH2n)(CO)2(dppv)2 (n = 2, 3; dppv = cis-1,2-C2H2(PPh2)2) form adducts with AlBr3 and B(C6F5)3, which adopt the "rotated structure" proposed for the active site of the Fe-only hydrogenases--the propanedithiolate is significantly more Lewis basic due to nonbonded interactions between the dithiolate strap and the ligands on Fe.
Justice
Aaron K
AK
Department of Chemistry, University of Illinois, Urbana, IL, USA.
Zampella
Giuseppe
G
De Gioia
Luca
L
Rauchfuss
Thomas B
TB
D004980:Ethane / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D058085:Iron Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D011407:Propane / Q000031:analogs & derivatives* / Q000737:chemistry; D012399:Rotation; D013057:Spectrum Analysis; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D058085:Iron Compounds; D013438:Sulfhydryl Compounds; C522648:propanedithiolate; D004980:Ethane; D011407:Propane