Title
Ruthenocene and cyclopentadienyl pyrrolyl ruthenium as precursors for ruthenium atomic layer deposition : a comparative study of dissociation enthalpies Ruthenocene and cyclopentadienyl pyrrolyl ruthenium as precursors for ruthenium atomic layer deposition : a comparative study of dissociation enthalpies
Author
Faculty/Department
Faculty of Sciences. Chemistry
Publication type
article
Publication
Subject
Chemistry
Source (journal)
Theoretical chemistry accounts: theory, computation, and modeling
Volume/pages
131(2012) :7 , 9 p.
ISSN
1432-881X
Article Reference
1238
ISI
000307274300003
Carrier
E-only publicatie
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
RuCp2 (ruthenocene) and RuCpPy (cyclopentadienyl pyrrolyl ruthenium) complexes are used in ruthenium (Ru) atomic layer deposition (ALD) but exhibit a markedly different reactivity with respect to the substrate and co-reactant. In search of an explanation, we report here the results of a comparative study of the heterolytic and homolytic dissociation enthalpy of these two ruthenium complexes, making use of either density functional theory (DFT) or multiconfigurational perturbation theory (CASPT2). While both methods predict distinctly different absolute dissociation enthalpies, they agree on the relative values between both molecules. A reduced heterolytic dissociation enthalpy is obtained for RuCpPy compared to RuCp2, although the difference obtained from CASPT2 (19.9 kcal/mol) is slightly larger than the one obtained with any of the DFT functionals (around 17 kcal/mol). Both methods also agree on the more pronounced stability of the Cp- ligand in RuCpPy than in RuCp2 (by around 9 kcal/mol with DFT and by 6 kcal/mol with CASPT2).
E-info
https://repository.uantwerpen.be/docman/iruaauth/dcc263/bd02652.pdf
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