Linked Life Data

19138109

Source:http://linkedlifedata.com/resource/pubmed/id/19138109

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
4
pubmed:dateCreated
2010-6-21
pubmed:abstractText
Catalytic dinitrogen reduction with the Schrock complex is still hampered by low turn-over numbers that are likely to result from a degradation of the chelate ligand. In this work, we investigate modifications of the original HIPTN(3)N ligand applied by Schrock and co-workers in catalytic reduction of dinitrogen with density functional methods. We focus on ligands that are substituted in the para position of the central phenyl ring of the terphenyl moieties and on a ligand where the bridging nitrogen is exchanged by phosphorus. In addition, results for tris(pyrrolyl-alpha-methyl)amine, tris(pyrrolyl-alpha-ethyl)amine, and tris[2-(3-xylyl-imidazol-2-ylidene)ethyl]amine are reported. For this study, we take into account the full ligands without approximating them by model systems. Reaction energies for the various derivatives of HIPTN(3)N are found to be similar to those of the unchanged parent system. However, the most promising results for catalysis are obtained for the [{tris[2-(3-xylyl-imidazol-2-ylidene)ethyl]amine}Mo](N(2)) complex. Feasibility of the exchange of NH(3) by N(2) is found to be the pivotal question whether a complex can become a potential catalyst or not. A structure-reactivity relationship is derived which allows for the convenient estimation of the reaction energy for the NH(3)/N(2) exchange reaction solely from the wavenumber of the N[triple bond]N stretching vibration. This relationship may guide experiments as soon as a dinitrogen Mo complex is formed.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Feb
pubmed:issn
1520-510X
pubmed:author
pubmed:issnType
Electronic
pubmed:day
16
pubmed:volume
48
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
1638-48
pubmed:year
2009
pubmed:articleTitle
Ligands for dinitrogen fixation at Schrock-type catalysts.
pubmed:affiliation
Laboratorium fur Physikalische Chemie, ETH Zürich, Wolfgang-Pauli-Str. 10, CH-8093 Zürich, Switzerland.
pubmed:publicationType
Journal Article