title: Chelate control of diiron(I) dithiolates relevant to the [Fe-Fe]- hydrogenase active site.
abstract: The reaction of Fe2(S2C2H4)(CO)6 with cis-Ph2PCH=CHPPh2 (dppv) yields Fe2(S2C2H4)(CO)4(dppv), 1(CO)4, wherein the dppv ligand is chelated to a single iron center. NMR analysis indicates that in 1(CO)4, the dppv ligand spans axial and basal coordination sites. In addition to the axial-basal isomer, the 1,3-propanedithiolate and azadithiolate derivatives exist as dibasal isomers. Density functional theory (DFT) calculations indicate that the axial-basal isomer is destabilized by nonbonding interactions between the dppv and the central NH or CH2 of the larger dithiolates. The Fe(CO)3 subunit in 1(CO)4 undergoes substitution with PMe3 and cyanide to afford 1(CO)3(PMe3) and (Et4N)[1(CN)(CO)3], respectively. Kinetic studies show that 1(CO)4 reacts faster with donor ligands than does its parent Fe2(S2C2H4)(CO)6. The rate of reaction of 1(CO)4 with PMe3 was first order in each reactant, k = 3.1 x 10(-4) M(-1) s(-1). The activation parameters for this substitution reaction, DeltaH = 5.8(5) kcal/mol and DeltaS = -48(2) cal/deg.mol, indicate an associative pathway. DFT calculations suggest that, relative to Fe2(S2C2H4)(CO)6, the enhanced electrophilicity of 1(CO)4 arises from the stabilization of a "rotated" transition state, which is favored by the unsymmetrically disposed donor ligands. Oxidation of MeCN solutions of 1(CO)3(PMe3) with Cp2FePF6 yielded [Fe2(S2C2H4)(mu-CO)(CO)2(dppv)(PMe3)(NCMe)](PF6)2. Reaction of this compound with PMe3 yielded [Fe2(S2C2H4)(mu-CO)(CO)(dppv)(PMe3)2(NCMe)](PF6)2.
authors.affiliation: Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: Aaron K
authors.initials: AK
authors.lastname: Justice
authors.forename: Giuseppe
authors.initials: G
authors.lastname: Zampella
authors.forename: Luca
authors.initials: L
authors.lastname: De Gioia
authors.forename: Thomas B
authors.initials: TB
authors.lastname: Rauchfuss
authors.forename: Jarl Ivar
authors.initials: JI
authors.lastname: van der Vlugt
authors.forename: Scott R
authors.initials: SR
authors.lastname: Wilson
mesh_terms: D001665:Binding Sites; D005296:Ferrous Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D006864:Hydrogenase / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D007506:Iron-Sulfur Proteins / Q000737:chemistry*; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D012015:Reference Standards; D012680:Sensitivity and Specificity; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D005296:Ferrous Compounds; D007506:Iron-Sulfur Proteins; D013438:Sulfhydryl Compounds; D007501:Iron; C118830:iron hydrogenase; D006864:Hydrogenase