Skip to main content
Journal cover image

Electronic structure of a paramagnetic {MNO}6 complex: MnNO 5,5-tropocoronand.

Publication ,  Journal Article
Tangen, E; Conradie, J; Franz, K; Friedle, S; Telser, J; Lippard, SJ; Ghosh, A
Published in: Inorganic chemistry
March 2010

Using density functional theory (OLYP/STO-TZP) calculations, we have investigated the electronic structure of [Mn(5,5-tropocoronand)(NO)], a rare paramagnetic {MNO}(6) complex. Experimental methods, including magnetic susceptibility measurements and high-field electron paramagnetic resonance spectroscopy, have not provided an unambiguous spin state assignment for this complex. In other respects, however, the compound was fully characterized, including by means of single-crystal X-ray structure determination. The optimized S = 1 OLYP geometry reproduced all key aspects of the trigonal-bipyramidal molecular structure, including a short Mn-N(O) distance (approximately 1.7 A) and an essentially linear MnNO angle. In contrast, the S = 0 and S = 2 optimized structures disagreed with the crystal structure in critical respects. Moreover, three different exchange-correlation functionals (OLYP, B3LYP, and B3LYP*) indicated an S = 1 ground state by a clear margin of energy. An examination of the Kohn-Sham MOs of this state indicated a primarily d(xz)(2)d(yz)(2)d(xy)(1)d(x(2)-z(2))(1) electronic configuration, where the z axis is identified with the nearly linear MnNO axis. The d(y(2)) orbital is formally unoccupied in this state, interacting, as it does, head-on with two tropocoronand nitrogens lying along the y axis, the pseudo-3-fold axis of the trigonal bipyramid. The doubly occupied d(xz) and d(yz) orbitals are in actuality d(pi)(Fe)-pi*(NO)-based pi-bonding molecular orbitals, the alpha and beta "components" of which are significantly offset spatially. This offset results in excess minority spin density on the NO unit. Thus, the OLYP/TZP atomic spin populations are Mn, 2.85; N(O), -0.52; and O, -0.35.

Duke Scholars

Published In

Inorganic chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

March 2010

Volume

49

Issue

6

Start / End Page

2701 / 2705

Related Subject Headings

  • Oxides
  • Molecular Structure
  • Models, Molecular
  • Manganese Compounds
  • Inorganic & Nuclear Chemistry
  • Electron Spin Resonance Spectroscopy
  • Crystallography, X-Ray
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
 

Citation

APA
Chicago
ICMJE
MLA
NLM
Tangen, E., Conradie, J., Franz, K., Friedle, S., Telser, J., Lippard, S. J., & Ghosh, A. (2010). Electronic structure of a paramagnetic {MNO}6 complex: MnNO 5,5-tropocoronand. Inorganic Chemistry, 49(6), 2701–2705. https://doi.org/10.1021/ic901860x
Tangen, Espen, Jeanet Conradie, Katherine Franz, Simone Friedle, Joshua Telser, Stephen J. Lippard, and Abhik Ghosh. “Electronic structure of a paramagnetic {MNO}6 complex: MnNO 5,5-tropocoronand.Inorganic Chemistry 49, no. 6 (March 2010): 2701–5. https://doi.org/10.1021/ic901860x.
Tangen E, Conradie J, Franz K, Friedle S, Telser J, Lippard SJ, et al. Electronic structure of a paramagnetic {MNO}6 complex: MnNO 5,5-tropocoronand. Inorganic chemistry. 2010 Mar;49(6):2701–5.
Tangen, Espen, et al. “Electronic structure of a paramagnetic {MNO}6 complex: MnNO 5,5-tropocoronand.Inorganic Chemistry, vol. 49, no. 6, Mar. 2010, pp. 2701–05. Epmc, doi:10.1021/ic901860x.
Tangen E, Conradie J, Franz K, Friedle S, Telser J, Lippard SJ, Ghosh A. Electronic structure of a paramagnetic {MNO}6 complex: MnNO 5,5-tropocoronand. Inorganic chemistry. 2010 Mar;49(6):2701–2705.
Journal cover image

Published In

Inorganic chemistry

DOI

EISSN

1520-510X

ISSN

0020-1669

Publication Date

March 2010

Volume

49

Issue

6

Start / End Page

2701 / 2705

Related Subject Headings

  • Oxides
  • Molecular Structure
  • Models, Molecular
  • Manganese Compounds
  • Inorganic & Nuclear Chemistry
  • Electron Spin Resonance Spectroscopy
  • Crystallography, X-Ray
  • 3403 Macromolecular and materials chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences