PMID- 27642746
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20180112
LR  - 20180112
IS  - 1521-3765 (Electronic)
IS  - 0947-6539 (Linking)
VI  - 22
IP  - 44
DP  - 2016 Oct 24
TI  - Exploring the Oxidative-Addition Pathways of Phenyl Chloride in the Presence of 
      Pd(II) Abnormal N-Heterocyclic Carbene Complexes: A DFT Study.
PG  - 15778-15790
LID - 10.1002/chem.201602735 [doi]
AB  - DFT calculations were performed to elucidate the oxidative addition mechanism of 
      the dimeric palladium(II) abnormal N-heterocyclic carbene complex 2 in the 
      presence of phenyl chloride and NaOMe base under the framework of a 
      Suzuki-Miyaura cross-coupling reaction. Pre-catalyst 2 undergoes facile, 
      NaOMe-assisted dissociation, which led to monomeric palladium(II) species 5, 6, 
      and 7, each of them independently capable of initiating oxidative addition 
      reactions with PhCl. Thereafter, three different mechanistic routes, path a, path 
      b, and path c, which originate from the catalytic species 5, 7, and 6, were 
      calculated at M06-L-D3(SMD)/LANL2TZ(f)(Pd)/6-311++G**//M06-L/LANL2DZ(Pd)/6-31+G* 
      level of theory. All studied routes suggested the rather uncommon Pd(II) /Pd(IV) 
      oxidative addition mechanism to be favourable under the ambient reaction 
      conditions. Although the Pd(0) /Pd(II) routes are generally facile, the final 
      reductive elimination step from the catalytic complexes were energetically 
      formidable. The Pd(II) /Pd(IV) activation barriers were calculated to be 11.3, 
      9.0, 26.7 kcal mol(-1) (DeltaDelta( not equal) G(L)(S-D3) ) more favourable than the Pd(II) /Pd(0) 
      reductive elimination routes for path a, path b, and path c, respectively. Out of 
      all the studied pathways, path a was the most feasible as it comprised of a 
      Pd(II) /Pd(IV) activation barrier of 24.5 kcal mol(-1) (DeltaG(L)(S-D3) ). To further 
      elucidate the origin of transition-state barriers, EDA calculations were 
      performed for some key saddle points populating the energy profiles.
CI  - (c) 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
FAU - Mondal, Totan
AU  - Mondal T
AD  - Department of Chemical Sciences, Indian Institute of Science Education and 
      Research Kolkata, Mohanpur -, 741 246, India.
FAU - De, Sriman
AU  - De S
AD  - Department of Chemical Sciences, Indian Institute of Science Education and 
      Research Kolkata, Mohanpur -, 741 246, India.
FAU - Maity, Bholanath
AU  - Maity B
AD  - Department of Chemical Sciences, Indian Institute of Science Education and 
      Research Kolkata, Mohanpur -, 741 246, India.
FAU - Koley, Debasis
AU  - Koley D
AD  - Department of Chemical Sciences, Indian Institute of Science Education and 
      Research Kolkata, Mohanpur -, 741 246, India. koley@iiserkol.ac.in.
LA  - eng
PT  - Journal Article
DEP - 20160919
PL  - Germany
TA  - Chemistry
JT  - Chemistry (Weinheim an der Bergstrasse, Germany)
JID - 9513783
OTO - NOTNLM
OT  - abnormal NHCs
OT  - density functional calculations
OT  - mechanism
OT  - oxidative addition
OT  - palladium
EDAT- 2016/10/21 06:00
MHDA- 2016/10/21 06:01
CRDT- 2016/09/20 06:00
PHST- 2016/06/09 00:00 [received]
PHST- 2016/10/21 06:00 [pubmed]
PHST- 2016/10/21 06:01 [medline]
PHST- 2016/09/20 06:00 [entrez]
AID - 10.1002/chem.201602735 [doi]
PST - ppublish
SO  - Chemistry. 2016 Oct 24;22(44):15778-15790. doi: 10.1002/chem.201602735. Epub 2016 
      Sep 19.