BROWSE

Related Researcher

Author's Photo

Rohde, Jan-Uwe
Transition Metal Chemistry
Research Interests
  • Inorganic chemistry, coordination chemistry, organometallic chemistry, chemical synthesis, catalysis, green chemistry, inorganic reaction mechanisms.

ITEM VIEW & DOWNLOAD

Axial ligand effects on the geometric and electronic structures of nonheme Oxoiron(IV) complexes

Cited 77 times inthomson ciCited 73 times inthomson ci
Title
Axial ligand effects on the geometric and electronic structures of nonheme Oxoiron(IV) complexes
Author
Jackson, Timothy A.Rohde, Jan-UweSeo, Mi SookSastri, Chivukula V.DeHont, RaymondStubna, AudriaOhta, TakehiroKitagawa, TeizoMunck, EckardNam, WonwooQue, Lawrence, Jr.
Keywords
Electronic structures; Ligand effects; Nonheme oxoiron complexes
Issue Date
2008-09
Publisher
AMER CHEMICAL SOC
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.130, no.37, pp.12394 - 12407
Abstract
A series of complexes [Fe(IV)(O)(TMC)(X)](+) (where X = OH(-), CF(3)CO(2)(-), N(3)(-), NCS(-), NCO(-), and CN(-)) were obtained by treatment of the well-characterized nonheme oxoiron(IV) complex [Fe(IV)(O)(TMC)-(NCMe)](2+) (TMC = tetramethylcyclam) with the appropriate NR(4)X salts. Because of the topology of the TMC macrocycle, the [Fe(IV)(O)(TMC)(X)]+ series represents an extensive collection of S = 1 oxoiron(IV) complexes that only differ with respect to the ligand trans to the oxo unit. Electronic absorption, Fe K-edge X-ray absorption, resonance Raman, and Mossbauer data collected for these complexes conclusively demonstrate that the characteristic spectroscopic features of the S = 1 Fe(IV)=O unit, namely, (i) the near-IR absorption properties, (ii) X-ray absorption pre-edge intensities, and (iii) quadrupole splitting parameters, are strongly dependent on the identity of the trans ligand. However. on the basis of extended X-ray absorption fine structure data, most [Fe(IV)(O)(TMC)(X)](+) species have Fe=O bond lengths similar to that of [Fe(IV)(O)(TMC)(NCMe)](2+) (1.66 +/- 0.02 angstrom). The mechanisms by which the trans ligands perturb the Fe(IV)=O unit were probed using density functional theory (DFT) computations, yielding geometric and electronic structures in good agreement with our experimental data. These calculations revealed that the trans ligands modulate the energies of the Fe=O sigma- and pi-antibonding molecular orbitals, causing the observed spectroscopic changes. Time-dependent DFT methods were used to aid in the assignment of the intense near-UV absorption bands found for the oxoiron(IV) complexes with trans N(3)(-), NCS(-), and NCO(-) ligands as X(-)-to-Fe(IV)=O charge-transfer transitions, thereby rationalizing the resonance enhancement of the nu(Fe=O) mode upon excitation of these chromophores
URI
Go to Link
DOI
10.1021/ja8022576
ISSN
0002-7863
Appears in Collections:
PHY_Journal Papers
Files in This Item:
ja8022576.pdf Download

find_unist can give you direct access to the published full text of this article. (UNISTARs only)

Show full item record

qrcode

  • mendeley

    citeulike

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

MENU