title: An evaluation by density functional theory of M-M interactions in organometallic clusters with the [Fe(3)MoS(3)](2+) cores.
abstract: Density functional theory calculations were carried out on the structurally characterized [(Cl(4)-cat)Mo(py)Fe(3)S(3) (CO)(4)(P(n)Pr(3))(3)], A, and (Cl(4)-cat)Mo(py)Fe(3)S(3)(CO)(6)(PEt(3))(2), B, and also on A(2)(-) and B(2+) clusters. The Fe-Fe distances in these molecules depend on the total number of valence electrons (60 e(-) in A and B(2)(+) and 62 e(-) in A(2)(-) and B) and undergo great structural changes upon addition or removal of electrons. The changes are consistent with known electron-counting rules in organometallic chemistry. The weak nature of the Fe-Fe bonding interactions in these clusters is apparent in the very similar energies of states with widely different Fe-Fe distances.
authors.affiliation: Departments of Chemistry, University of Karlsruhe, Karlsruhe, Germany, and University of Michigan, Ann Arbor, Michigan 48109-1055, USA.
authors.forename: Paola
authors.initials: P
authors.lastname: Nava
authors.forename: Jaehong
authors.initials: J
authors.lastname: Han
authors.forename: Reinhart
authors.initials: R
authors.lastname: Ahlrichs
authors.forename: Dimitri
authors.initials: D
authors.lastname: Coucouvanis
mesh_terms: D002396:Catechols / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D016000:Cluster Analysis; D003035:Cobalt / Q000737:chemistry; D018360:Crystallography, X-Ray; D004583:Electrons; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D009591:Nitrogenase / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011621:Pteridines / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry*
chemical_list: D002396:Catechols; D002712:Chlorides; D008024:Ligands; D009942:Organometallic Compounds; D011621:Pteridines; D011725:Pyridines; D003035:Cobalt; D013455:Sulfur; D008982:Molybdenum; D007501:Iron; D009591:Nitrogenase