Quick Search:

uzh logo
Browse by:

Zurich Open Repository and Archive

Maintenance: Tuesday, July the 26th 2016, 07:00-10:00

ZORA's new graphical user interface will be relaunched (For further infos watch out slideshow ZORA: Neues Look & Feel). There will be short interrupts on ZORA Service between 07:00am and 10:00 am. Please be patient.

Permanent URL to this publication: http://dx.doi.org/10.5167/uzh-3179

Reiher, M; Kirchner, B; Hutter, J; Sellmann, D; Hess, B A (2004). A photochemical activation scheme of inert dinitrogen by dinuclear Ru(II) and Fe(II) complexes. Chemistry - A European Journal, 10(18):4443-4453.

[img] PDF - Registered users only
View at publisher


A general photochemical activation process of inert dinitrogen coordinated to two metal centers is presented on the basis of high-level DFT and ab initio calculations. The central feature of this activation process is the occupation of an antibonding pi{*} orbital upon electronic excitation from the singlet ground state S-0 to the first excited singlet state S-1. Populating the antibonding LUMO weakens the triple bond of dinitrogen. After a vertical excitation, the excited complex may structurally relax in the S-1 state and approaches its minimum structure in the S-1 state. This excited-state minimum structure features the dinitrogen bound in a diazenoid form, which exhibits a double bond and two lone pairs localized at the two nitrogen atoms, ready to be protonated. Reduction and de-excitation then yield the corresponding diazene complex; its generation represents the essential step in a nitrogen fixation and reduction protocol. The consecutive process of excitation, protonation, and reduction may be rearranged in any experimentally appropriate order. The protons needed for the reaction from dinitrogen to diazene can be provided by the ligand sphere of the complexes, which contains sulfur atoms acting as proton acceptors. These protonated thiolate functionalities bring protons close to the dinitrogen moiety. Because protonation does not change the pi{*}-antibonding character of the LUMO, the universal and well-directed character of the photochemical activation process makes it possible to protonate the dinitrogen complex before it is irradiated. The pi{*}-antibonding LUMO plays the central role in the activation process, since the diazenoid structure was obtained by excitation from various occupied orbitals as well as by a direct two-electron reduction (without photochemical activation) of the complex; that is, the important bending of N-2 towards a diazenoid conformation can be achieved by populating the pi{*}-antibonding LUMO.


24 citations in Web of Science®
27 citations in Scopus®
Google Scholar™



1 download since deposited on 27 Mar 2009
0 downloads since 12 months

Detailed statistics

Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Date:September 2004
Deposited On:27 Mar 2009 09:52
Last Modified:05 Apr 2016 12:26
Publisher DOI:10.1002/chem.200400081
PubMed ID:15378622

Users (please log in): suggest update or correction for this item

Repository Staff Only: item control page