Unraveling the Electronic Structures of Low-Valent Naphthalene and Anthracene Iron Complexes: X-ray, Spectroscopic, and Density Functional Theory Studies

被引：30

作者：

Schnoeckelborg, Eva-Maria ^{[1
]}

Khusniyarov, Marat M. ^{[3
]}

de Bruin, Bas ^{[4
]}

Hartl, Frantisek ^{[5
]}

Langer, Thorsten ^{[1
]}

Eul, Matthias ^{[1
]}

Schulz, Stephen ^{[1
]}

Poettgen, Rainer ^{[1
]}

Wolf, Robert ^{[1
,2
]}

机构：

[1] Univ Munster, Inst Inorgan & Analyt Chem, D-48149 Munster, Germany

[2] Univ Regensburg, Inst Inorgan Chem, D-93040 Regensburg, Germany

[3] Univ Erlangen Nurnberg, Dept Chem & Pharm, D-91058 Erlangen, Germany

[4] Univ Amsterdam, Vant Hoff Inst Mol Sci, NL-1098 XH Amsterdam, Netherlands

[5] Univ Reading, Dept Chem, Reading RG6 6AD, Berks, England

来源：

INORGANIC CHEMISTRY | 2012年 / 51卷 / 12期

关键词：

ORDER REGULAR APPROXIMATION; RICH TRANSITION-METALS; ARENE LIGAND-EXCHANGE; REACTIVE PI-COMPLEXES; TRIPLE ZETA VALENCE; GAUSSIAN-BASIS SETS; ISOCYANIDE COMPLEXES; CORRELATION-ENERGY; CRYSTAL-STRUCTURE; AB-INITIO;

D O I：

10.1021/ic300366m

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Naphthalene and anthracene transition metalates are potent reagents, but their electronic structures have remained poorly explored. A study of four Cp*-substituted iron complexes (Cp* = pentamethylcyclopentadienyl) now gives rare insight into the bonding features of such species. The highly oxygen- and water-sensitive compounds [K(18-crown-6){Cp*Fe(eta(4)-C10H8)}] (K1), [K(18-crown-6)[Cp*Fe(eta(4)-C14H10)}] (K2), [Cp*Fe(eta(4)-C10H8)] (1), and [Cp*Fe(eta(4)-C14H10)] (2) were synthesized and characterized by NMR, UV-vis, and Fe-57 Mossbauer spectroscopy. The paramagnetic complexes 1 and 2 were additionally characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility measurements. The molecular structures of complexes K1, K2, and 2 were determined by single-crystal X-ray crystallography. Cyclic voltammetry of 1 and 2 and spectroelectrochemical experiments revealed the redox properties of these complexes, which are reversibly reduced to the monoanions [Cp*Fe(eta(4)-C10H8)](-) (1(-)) and [Cp*Fe(eta(4)-C14H10)](-) (2(-)) and reversibly oxidized to the cations [Cp*Fe(eta(4)-C10H8)](+) (1(+)) and [Cp*Fe(eta(4)-C14H10](+) (2(+)). Reduced orbital charges and spin densities of the naphthalene complexes 1(-/0/+) and the anthracene derivatives 2(-/0/+) were obtained by density functional theory (DFT) methods. Analysis of these data suggests that the electronic structures of the anions 1(-) and 2(-) are best represented by low-spin Fe-II ions coordinated by anionic Cp* and dianionic naphthalene and anthracene ligands. The electronic structures of the neutral complexes 1 and 2 may be described by a superposition of two resonance configurations which, on the one hand, involve a low-spin Fe-I ion coordinated by the neutral naphthalene or anthracene ligand L, and, on the other hand, a low-spin Fe-II ion coordinated to a ligand radical L. Our study thus reveals the redox noninnocent character of the naphthalene and anthracene ligands, which effectively stabilize the iron atoms in a low formal, but significantly higher spectroscopic oxidation state.

引用

页码：6719 / 6730

页数：12

共 50 条

[21] Investigation of the electronic structure of diphenylsilane using the density functional theory method and X-ray emission spectroscopy
T. N. Danilenko
M. M. Tatevosyan
V. G. Vlasenko
Physics of the Solid State, 2012, 54 : 2100 - 2105
[22] An x-ray emission and density functional theory study of the electronic structure of Zn1-xMnxS
Wilks, R. G.
Kurmaev, E. Z.
Sandratskii, L. M.
Postnikov, A. V.
Finkelstein, L. D.
Surkova, T. P.
Lopez-Rivera, S. A.
Moewes, A.
JOURNAL OF PHYSICS-CONDENSED MATTER, 2006, 18 (46) : 10405 - 10412
[23] Electronic structure of Ni and Mo silicides investigated by x-ray emission spectroscopy and density functional theory
Jarrige, Ignace
Capron, Nathalie
Jonnard, Philippe
PHYSICAL REVIEW B, 2009, 79 (03):
[24] Investigation of the electronic structure of diphenylsilane using the density functional theory method and X-ray emission spectroscopy
Danilenko, T. N.
Tatevosyan, M. M.
Vlasenko, V. G.
PHYSICS OF THE SOLID STATE, 2012, 54 (10) : 2100 - 2105
[25] Electronic Structure of FeSe1-xTex Studied by X-ray Spectroscopy and Density Functional Theory
Perez, I.
Mcleod, J. A.
Green, R. J.
Escamilla, R.
Ortiz, V.
Moewes, A.
JOURNAL OF PHYSICAL CHEMISTRY C, 2014, 118 (43): : 25150 - 25157
[26] X-ray crystallographic and absorption spectroscopic analyses of structures of catecholato(pyridine) iron chloride complexes in relevance to functional model complexes for catechol 1,2-dioxygenases
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
不详
Inorg. Chim. Acta, (222-229):
[27] X-ray crystallographic and absorption spectroscopic analyses of structures of catecholato(pyridine)iron chloride complexes in relevance to functional model complexes for catechol 1,2-dioxygenases
Funabiki, T
Nagai, Y
Kojima, H
Tanaka, T
Yoshida, S
Masuda, H
INORGANICA CHIMICA ACTA, 1998, 276 (1-2) : 222 - 229
[28] INOR 566-Sulfur K-edge X-ray absorption spectroscopic and density functional theory studies of metal bis- and tris-dithiolene complexes
Tenderholt, Adam L.
Szilagyi, Robert K.
Holm, Richard H.
Hodgson, Keith O.
Hedman, Britt
Solomon, Edward I.
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2008, 236
[29] Resonant inelastic soft x-ray scattering, x-ray absorption spectroscopy, and density functional theory calculations of the electronic bulk band structure of CdS
Weinhardt, L.
Fuchs, O.
Umbach, E.
Heske, C.
Fleszar, A.
Hanke, W.
PHYSICAL REVIEW B, 2007, 75 (16):
[30] Electronic structure studies of Ni-X (X: B, S, P) alloys using x-ray photoelectron spectroscopy, x-ray induced Auger electron spectroscopy and density functional theory calculations
Diplas, S.
Lovvik, O. M.
JOURNAL OF PHYSICS-CONDENSED MATTER, 2009, 21 (24)

← 1 2 3 4 5 →