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Ligand Bond Energies in cis- and trans-[L-Pd(PH(3))(2)Cl](+) Complexes from Coupled Cluster Theory (CCSD(T)) and Density Functional Theory.
MedLine Citation:
PMID:  23194426     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
The Pd-L ligand bond dissociation energies (BDEs) of cis- and trans-[L-Pd(PH(3))(2)Cl](+) were predicted using coupled cluster CCSD(T) theory and a variety of density functional theory (DFT) functionals at the B3LYP optimized geometries. trans-[L-Pd(PH(3))(2)Cl](+) is the more stable isomer when Pd forms a donor-acceptor bond with a C atom of the ligand, including the π-bond in norbornene; for the remaining complexes, the cis-[L-Pd(PH(3))(2)Cl](+) isomer is substantially lower in energy. For cis-[L-Pd (PH(3))(2)Cl](+) complexes, the Pd-L bond energies are 28 kcal/mol for CO; ∼40 kcal/mol for AH(3) (A = N, P, As, and Sb), norbornene, and CH(3)CN; and ∼53 kcal/mol for CH(3)NC, pyrazole, pyridine, and tetrahydrothiophene at the CCSD(T) level. When Pd forms a donor-acceptor bond with the C atom in the ligand (i.e., CO, CH(3)NC, and the π-bond in norbornene), the Pd-L bond energies for trans-[L-Pd(PH(3))(2)Cl](+) are generally ∼10 kcal/mol greater than those for cis-[L-Pd(PH(3))(2)Cl](+) with the same L; for the remaining ligands, the ligand bond energy increases are ∼3-5 kcal/mol from the cis-isomer to the trans-isomer. The benchmarks show that the dispersion-corrected hybrid, generalized gradient approximation, DFT functional ω-B97X-D is the best one to use for this system. Use of the ω-B97X-D/aD functional gives predicted BDEs within 1 kcal/mol of the CCSD(T)/aug-cc-pVTZ BDEs for cis-[L-Pd(PH(3))(2)Cl](+) and 1.5 kcal/mol for trans-[L-Pd(PH(3))(2)Cl](+).
Authors:
Mingyang Chen; Raluca Craciun; Norris Hoffman; David A Dixon
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-11-29
Journal Detail:
Title:  Inorganic chemistry     Volume:  -     ISSN:  1520-510X     ISO Abbreviation:  Inorg Chem     Publication Date:  2012 Nov 
Date Detail:
Created Date:  2012-11-30     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0366543     Medline TA:  Inorg Chem     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Chemistry Department, The University of Alabama , Shelby Hall, Box 870336, Tuscaloosa, Alabama 35487-0336, United States.
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