PMID- 26636218
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20151207
LR  - 20151205
IS  - 1549-9618 (Print)
IS  - 1549-9618 (Linking)
VI  - 3
IP  - 6
DP  - 2007 Nov
TI  - Carbon-Hydrogen Bond Activation in Hydridotris(pyrazolyl)borate Platinum(IV) 
      Complexes:  Comparison of Density Functionals, Basis Sets, and Bonding Patterns.
PG  - 2268-81
LID - 10.1021/ct700120d [doi]
AB  - The reaction mechanism for the cycle beginning with the reductive elimination 
      (RE) of methane from kappa(3)-TpPt(IV)(CH3)2H (1) (Tp = hydridotris(pyrazolyl)borate) 
      and subsequent oxidative addition (OA) of benzene to form finally 
      kappa(3)-TpPt(IV)(Ph)2H (19) was investigated by density functional theory (DFT). Two 
      mechanistic steps are of particular interest, namely the barrier to C-H coupling 
      (barrier 1 - Ba1) and the barrier to methane release (barrier 2 - Ba2). For 31 
      density functionals, the calculated values for Ba1 and Ba2 were benchmarked 
      against the experimentally reported values of 26 (Ba1) and 35 (Ba2) kcal.mol(-1), 
      respectively. Specifically, the values for Ba1 and Ba2, calculated at the 
      B3LYP/double-zeta plus polarization level of theory, are 24.6 and 34.3 kcal.mol(-1), 
      respectively. Overall, the best performing functional was BPW91 where the mae 
      associated with the calculated values of the two barriers is 0.68 kcal.mol(-1). 
      The calculated B3LYP values of Ba1 ranged between 20 and 26 kcal.mol(-1) for 12 
      effective core potential basis sets for platinum and 29 all-electron basis sets 
      for the first row elements. Polarization functions for the first row elements 
      were important for accurate values, but the addition of diffuse functions to 
      non-hydrogen (+) and hydrogen atoms (++) had little effect on the calculated 
      values. Basis set saturation was achieved with APNO basis sets utilized for 
      first-row atoms. Bader's "Atoms in Molecules" was used to analyze the electron 
      density of several complexes, and the electron density at the Pt-Nax bond 
      critical point (trans to the active site for C-H coupling) varied over a wider 
      range than any of the other Pt-N bonds.
FAU - Vastine, Benjamin Alan
AU  - Vastine BA
AD  - Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, 
      Texas 77841-3012.
FAU - Webster, Charles Edwin
AU  - Webster CE
AD  - Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, 
      Texas 77841-3012.
FAU - Hall, Michael B
AU  - Hall MB
AD  - Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, 
      Texas 77841-3012.
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Chem Theory Comput
JT  - Journal of chemical theory and computation
JID - 101232704
EDAT- 2007/11/01 00:00
MHDA- 2007/11/01 00:01
CRDT- 2015/12/05 06:00
PHST- 2015/12/05 06:00 [entrez]
PHST- 2007/11/01 00:00 [pubmed]
PHST- 2007/11/01 00:01 [medline]
AID - 10.1021/ct700120d [doi]
PST - ppublish
SO  - J Chem Theory Comput. 2007 Nov;3(6):2268-81. doi: 10.1021/ct700120d.