PMID- 36469940
OWN - NLM
STAT- MEDLINE
DCOM- 20221215
LR  - 20221222
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Linking)
VI  - 144
IP  - 49
DP  - 2022 Dec 14
TI  - Nickel-Catalyzed Homologation of Vinylidene Difluoride (CH(2) horizontal lineCF(2)): Selective 
      beta-F vs beta-H Elimination.
PG  - 22713-22721
LID - 10.1021/jacs.2c10448 [doi]
AB  - Hydrofluoroolefins (HFOs) constitute the newest generation of fluorocarbon 
      refrigerants and foam-blowing agents due to their reduced global warming 
      potential vs their saturated analogues. To identify new synthetic routes to HFOs, 
      we show that reactions of bulky Ni(0) phosphine and -NHC complexes with 
      vinylidene difluoride (VF2) afford mu-fluoro-1,1,3-trifluorobut-3-enyl Ni 
      complexes. Moreover, addition of triisopropylsilane allows for reductive 
      elimination of the reduced product horizontal line 2,4,4-trifluoro-1-butene horizontal line demonstrating the 
      Ni-catalyzed hydrodefluorodimerization of VF2. Accompanying DFT calculations 
      identify the T-shaped nickelacyclopentane intermediate that spontaneously 
      undergoes selective intramolecular beta-F (vs beta-H) elimination.
FAU - Sicard, Alexandre J
AU  - Sicard AJ
AD  - Department of Chemistry and Biomolecular Sciences and Centre for Catalysis 
      Research and Innovation, University of Ottawa, 30 Marie Curie, Ottawa, Ontario 
      K1N 6N5, Canada.
FAU - Ghaffari, Behnaz
AU  - Ghaffari B
AD  - Department of Chemistry and Biomolecular Sciences and Centre for Catalysis 
      Research and Innovation, University of Ottawa, 30 Marie Curie, Ottawa, Ontario 
      K1N 6N5, Canada.
FAU - Gabidullin, Bulat M
AU  - Gabidullin BM
AUID- ORCID: 0000-0002-2197-4125
AD  - Faculty of Science, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
FAU - Ovens, Jeffrey S
AU  - Ovens JS
AD  - Faculty of Science, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
FAU - Hughes, Russell P
AU  - Hughes RP
AUID- ORCID: 0000-0002-1891-6530
AD  - Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, United 
      States.
FAU - Baker, R Tom
AU  - Baker RT
AUID- ORCID: 0000-0002-1133-7149
AD  - Department of Chemistry and Biomolecular Sciences and Centre for Catalysis 
      Research and Innovation, University of Ottawa, 30 Marie Curie, Ottawa, Ontario 
      K1N 6N5, Canada.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20221205
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
RN  - 7OV03QG267 (Nickel)
SB  - IM
MH  - *Nickel
MH  - Catalysis
EDAT- 2022/12/06 06:00
MHDA- 2022/12/16 06:00
CRDT- 2022/12/05 17:13
PHST- 2022/12/06 06:00 [pubmed]
PHST- 2022/12/16 06:00 [medline]
PHST- 2022/12/05 17:13 [entrez]
AID - 10.1021/jacs.2c10448 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2022 Dec 14;144(49):22713-22721. doi: 10.1021/jacs.2c10448. Epub 
      2022 Dec 5.