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Computational analysis of ^{47/49}Ti NMR shifts and electric field gradient tensors of half-titanocene complexes : structure-bonding-property relationships

Computational analysis of ^{47/49}Ti NMR shifts and ...

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dc.contributor.author Srebro-Hooper, Monika [SAP13036569] pl
dc.contributor.author Autschbach, Jochen pl
dc.date.accessioned 2015-06-18T08:38:53Z
dc.date.available 2015-06-18T08:38:53Z
dc.date.issued 2013 pl
dc.identifier.issn 0947-6539 pl
dc.identifier.uri http://ruj.uj.edu.pl/xmlui/handle/item/9783
dc.language eng pl
dc.title Computational analysis of ^{47/49}Ti NMR shifts and electric field gradient tensors of half-titanocene complexes : structure-bonding-property relationships pl
dc.type JournalArticle pl
dc.description.physical 12018-12033 pl
dc.description.additional Na publikacji autorka Srebro-Hooper Monika podpisana jako Srebro Monika. pl
dc.abstract.en Metal NMR shielding and electric-field gradient (EFG) tensors are examined by quantum-chemical calculations for a set of 14 titanium(IV) complexes. Benchmarks are performed for titanocene chlorides that have been characterized recently by solid-state NMR experiments, focusing on the dependence of TiIV NMR parameters on the computational model in terms of the choice of the density functional, and considering molecular clusters versus infinite-periodic solid. Nearest-neighbor and long-range effects in the solid state are found to influence NMR parameters in systems without spatially extended ligands. Bulky ligands increase the fraction of local structure and bonding information encoded in the EFG tensors by reducing intermolecular interactions. Next, Ti shielding constants and EFG tensors for a variety of olefin (co)polymerization catalysts are analyzed in terms of contributions from localized molecular orbitals representing Lewis bonds and lone pairs. Direct links between the observed theoretical trends and the local bonding environment around the Ti metal center are found. A specific dependence of the Ti EFG tensors on the exact arrangement and type of surrounding bonds is demonstrated, providing a basis for further studies on solid-supported titanium catalytic systems. pl
dc.description.volume 19 pl
dc.description.number 36 pl
dc.identifier.doi 10.1002/chem.201301301 pl
dc.identifier.eissn 1521-3765 pl
dc.title.journal Chemistry : a European Journal pl
dc.language.container eng pl
dc.affiliation Wydział Chemii : Zakład Chemii Teoretycznej im. K. Gumińskiego pl
dc.subtype Article pl
dc.rights.original bez licencji pl
.pointsMNiSW [2013 A]: 40


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