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Title: [(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2–: Foundations toward the Development of Trifluoromethylations at Unsupported Nickel

Journal Article · · Inorganic Chemistry
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5];  [3]; ORCiD logo [6]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Lehigh Univ., Bethlehem, PA (United States)
  2. Cornell Univ., Ithaca, NY (United States)
  3. Russian Academy of Sciences (RAS), Kazan (Russian Federation)
  4. Stanford Univ., CA (United States)
  5. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  6. Univ. of Hawaii at Manoa, Honolulu, HI (United States)
+ Show Author Affiliations

Nickel anions [(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2– were prepared by the formal addition of 3 and 4 equiv, respectively, of AgCF3 to [(dme)NiBr2] in the presence of the [PPh4]+ counterion. Detailed insights into the electronic properties of these new compounds were obtained through the use of density functional theory (DFT) calculations, spectroscopy-oriented configuration interaction (SORCI) calculations, X-ray absorption spectroscopy, and cyclic voltammetry. The data collectively show that trifluoromethyl complexes of nickel, even in the most common oxidation state of nickel(II), are highly covalent systems whereby a hole is distributed on the trifluoromethyl ligands, surprisingly rendering the metal to a physically more reduced state. In the cases of [(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2-, these complexes are better physically described as d9 metal complexes. [(MeCN)Ni(CF3)3]- is electrophilic and reacts with other nucleophiles such as phenoxide to yield the unsupported [(PhO)Ni(CF3)3]2– salt, revealing the broader potential of [(MeCN)Ni(CF3)3]- in the development of “ligandless” trifluoromethylations at nickel. Proof-in-principle experiments show that the reaction of [(MeCN)Ni(CF3)3]- with an aryl iodonium salt yields trifluoromethylated arene, presumably via a high-valent, unsupported, and formal organonickel(IV) intermediate. Evidence of the feasibility of such intermediates is provided with the structurally characterized [PPh4]2[Ni(CF3)4(SO4)], which was derived through the two-electron oxidation of [Ni(CF3)4]2–.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lehigh Univ., Bethlehem, PA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-76SF00515; CHE-1454455; SC0009363; P41GM103393
OSTI ID:
1646811
Alternate ID(s):
OSTI ID: 1696919
Journal Information:
Inorganic Chemistry, Vol. 59, Issue 13; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Metals
Ligands
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Trifluoromethyl
Nickel