title: Variable pi-bonding in iron(II) porphyrinates with nitrite, CO, and tert-butyl isocyanide: characterization of [Fe(TpivPP)(NO2)(CO)]-.
abstract: The addition of the strongly pi-bonding ligands CO or tert-butyl isocyanide to the low-spin five-coordinate iron(II) nitrite species [Fe(TpivPP)(NO2)]- (TpivPP = picket fence porphyrin) gives two new six-coordinate species [Fe(TpivPP)(NO2)(CO)]- and [Fe(TpivPP)(NO2)(t-BuNC)]-. These species have been characterized by single-crystal structure determinations and by UV-vis, IR, and Mössbauer spectroscopies. All evidence shows that in the mixed-ligand iron(II) porphyrin species, [Fe(TpivPP)(NO2)(CO)]-, the two trans, pi-accepting ligands CO and nitrite compete for pi density. The CO ligand however dominates the bonding. The Fe-N(NO2) bond lengths for the two independent anions in the unit cell at 2.006(4) and 2.009(4) A are lengthened compared to other nitrite species with either no trans ligands or non-pi-accepting trans ligands to nitrite. The Fe-C(CO) bond lengths are 1.782(4) A and 1.789(5) A for the two anions. The two Fe-C-O angles at 175.5(4) and 177.5(4) degrees are essentially linear in both anions. The quadrupole splitting for [Fe(TpivPP)(NO2)(CO)]- was determined to be 0.32 mm/s, and the isomer shift was 0.18 mm/s at room temperature in zero applied field. Both of the Mössbauer parameters are much smaller than those found for six-coordinate low-spin iron(II) porphyrinates with neutral nitrogen-donating ligands as well as iron(II) nitro complexes. However, the Mössbauer parameters are typical of other six-coordinate CO porphyrinates signifying that CO is the more dominant ligand. The CO stretching frequency of 1974 cm(-1) is shifted only slightly to higher energy compared to six-coordinate CO complexes with neutral nitrogen-donor ligands trans to CO. Crystal data for [K(222)][Fe(TpivPP)(NO2)(CO)].1/2C6H5Cl: monoclinic, space group P2(1)/c, Z = 8, a = 33.548(6) A, b = 18.8172(15) A, c = 27.187(2) A, beta = 95.240(7) degrees, V = 17091(4) A3.
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, USA.
authors.forename: Habib
authors.initials: H
authors.lastname: Nasri
authors.forename: Mary K
authors.initials: MK
authors.lastname: Ellison
authors.forename: Maoyu
authors.initials: M
authors.lastname: Shang
authors.forename: Charles E
authors.initials: CE
authors.lastname: Schulz
authors.forename: W Robert
authors.initials: WR
authors.lastname: Scheidt
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry*; D005290:Ferric Compounds / Q000737:chemistry; D005296:Ferrous Compounds / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D008665:Metalloporphyrins / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry*; D009573:Nitrites / Q000737:chemistry*
chemical_list: D005290:Ferric Compounds; D005296:Ferrous Compounds; D008024:Ligands; D008665:Metalloporphyrins; D009570:Nitriles; D009573:Nitrites; C099535:tert-butyl isocyanide; D002248:Carbon Monoxide; D007501:Iron