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**Gutmann, T. and Schweitzer, A. and Wächtler, M. and Breitzke, H. and Blichholz, A. and Plass, W. and Buntkowsky, G.** (2008):

*DFT Calculations of (51)V Solid-State NMR Parameters of Vanadium(V) Model Complexes.*

In: Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics, 222 (8-9), pp. 1389-1406. [Article]

## Abstract

Two cis-dioxovanadium(V) complexes and three monoxovanadium(V) complexes with different coordination numbers and ligand Spheres. serving as model complexes for vanadium haloperoxidases, were studied by (51)V solid-state NMR spectroscopy. The most important (51)V solid-state NMR parameters (quadrupolar coupling constant C(Q), asymmetry of the EFG tensor eta(Q), isotropic chemical shift delta(iso), chemical shift anisotropy delta(sigma), asymmetry of the CSA tensor eta(sigma) and the Euler angles alpha, beta and gamma) describing the quadrupolar and chemical shift anisotropy interactions were determined theoretically with DFT methods employing the B3LYP functional and experimentally using genetic fitting algorithms. Calculations of delta(iso) values were treated with different referencing values of VOCl(3) computed with different-sized basis Sets using the "counterpoise method". The calculated C(Q) values were discussed in terms of the quadrupolar moment Q. Absolute tensor orientations of CSA and EFG tensors were computed by DFT. These orientations were found to correlate to structural features of the model complexes.

Item Type: | Article |
---|---|

Erschienen: | 2008 |

Creators: | Gutmann, T. and Schweitzer, A. and Wächtler, M. and Breitzke, H. and Blichholz, A. and Plass, W. and Buntkowsky, G. |

Title: | DFT Calculations of (51)V Solid-State NMR Parameters of Vanadium(V) Model Complexes |

Language: | English |

Abstract: | Two cis-dioxovanadium(V) complexes and three monoxovanadium(V) complexes with different coordination numbers and ligand Spheres. serving as model complexes for vanadium haloperoxidases, were studied by (51)V solid-state NMR spectroscopy. The most important (51)V solid-state NMR parameters (quadrupolar coupling constant C(Q), asymmetry of the EFG tensor eta(Q), isotropic chemical shift delta(iso), chemical shift anisotropy delta(sigma), asymmetry of the CSA tensor eta(sigma) and the Euler angles alpha, beta and gamma) describing the quadrupolar and chemical shift anisotropy interactions were determined theoretically with DFT methods employing the B3LYP functional and experimentally using genetic fitting algorithms. Calculations of delta(iso) values were treated with different referencing values of VOCl(3) computed with different-sized basis Sets using the "counterpoise method". The calculated C(Q) values were discussed in terms of the quadrupolar moment Q. Absolute tensor orientations of CSA and EFG tensors were computed by DFT. These orientations were found to correlate to structural features of the model complexes. |

Journal or Publication Title: | Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics |

Journal volume: | 222 |

Number: | 8-9 |

Uncontrolled Keywords: | solid-state nmr vanadium haloperoxidase dft quadrupolar interaction chemical shift anisotropy substituted n-salicylidenehydrazides anisotropic shielding tensors aluminum orthovanadate alvo4 density-functional theory gaussian-basis sets x-ray-structure supramolecular interactions dependent haloperoxidases oxovanadium(v) complexes relative orientation |

Divisions: | 07 Department of Chemistry 07 Department of Chemistry > Physical Chemistry |

Date Deposited: | 27 Oct 2014 20:41 |

Official URL: | http://apps.webofknowledge.com/full_record.do?product=WOS&se... |

Additional Information: | 376CU Times Cited:14 Cited References Count:71 |

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