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

Abstract

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]+ counter-ion. 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–.

Authors:
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)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lehigh Univ., Bethlehem, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1646811
Alternate Identifier(s):
OSTI ID: 1696919
Grant/Contract Number:  
AC02-76SF00515; CHE-1454455; SC0009363; P41GM103393
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 59; Journal Issue: 13; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Metals; Ligands; Oxidation; Trifluoromethyl; Nickel

Citation Formats

Shreiber, Scott T., DiMucci, Ida M., Khrizanforov, Mikhail N., Titus, Charles J., Nordlund, Dennis, Dudkina, Yulia, Cramer, Roger E., Budnikova, Yulia, Lancaster, Kyle M., and Vicic, David A. [(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2–: Foundations toward the Development of Trifluoromethylations at Unsupported Nickel. United States: N. p., 2020. Web. https://doi.org/10.1021/acs.inorgchem.0c01020.
Shreiber, Scott T., DiMucci, Ida M., Khrizanforov, Mikhail N., Titus, Charles J., Nordlund, Dennis, Dudkina, Yulia, Cramer, Roger E., Budnikova, Yulia, Lancaster, Kyle M., & Vicic, David A. [(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2–: Foundations toward the Development of Trifluoromethylations at Unsupported Nickel. United States. https://doi.org/10.1021/acs.inorgchem.0c01020
Shreiber, Scott T., DiMucci, Ida M., Khrizanforov, Mikhail N., Titus, Charles J., Nordlund, Dennis, Dudkina, Yulia, Cramer, Roger E., Budnikova, Yulia, Lancaster, Kyle M., and Vicic, David A. Tue . "[(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2–: Foundations toward the Development of Trifluoromethylations at Unsupported Nickel". United States. https://doi.org/10.1021/acs.inorgchem.0c01020. https://www.osti.gov/servlets/purl/1646811.
@article{osti_1646811,
title = {[(MeCN)Ni(CF3)3]- and [Ni(CF3)4]2–: Foundations toward the Development of Trifluoromethylations at Unsupported Nickel},
author = {Shreiber, Scott T. and DiMucci, Ida M. and Khrizanforov, Mikhail N. and Titus, Charles J. and Nordlund, Dennis and Dudkina, Yulia and Cramer, Roger E. and Budnikova, Yulia and Lancaster, Kyle M. and Vicic, David A.},
abstractNote = {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]+ counter-ion. 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–.},
doi = {10.1021/acs.inorgchem.0c01020},
journal = {Inorganic Chemistry},
number = 13,
volume = 59,
place = {United States},
year = {2020},
month = {6}
}

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Works referenced in this record:

Synthesis and X-ray structure of bis(trifluoromethyl)(N,N-diethyldithiocarbamato)-copper; a remarkably stable perfluoroalkylcopper(III) complex
journal, January 1989

  • Willert-Porada, Monika A.; Burton, Donald J.; Baenziger, Norman C.
  • Journal of the Chemical Society, Chemical Communications, Issue 21
  • DOI: 10.1039/c39890001633

Synthese und Struktur überraschend stabiler Tetrakis(trifluormethyl)cuprat(III)-Salze
journal, October 1993

  • Naumann, Dieter; Roy, Thomas; Tebbe, Karl-Friedrich
  • Angewandte Chemie, Vol. 105, Issue 10
  • DOI: 10.1002/ange.19931051048

From Widely Accepted Concepts in Coordination Chemistry to Inverted Ligand Fields
journal, June 2016


σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal Ni IV
journal, July 2019

  • Steen, Jelte S.; Knizia, Gerald; Klein, Johannes E. M. N.
  • Angewandte Chemie International Edition, Vol. 58, Issue 37
  • DOI: 10.1002/anie.201906658

Elusiveness of CuIII Complexation; Preference for Trifluoromethyl Oxidation in the Formation of[CuI(CF3)4]− Salts
journal, January 1995

  • Snyder, James P.
  • Angewandte Chemie International Edition in English, Vol. 34, Issue 1
  • DOI: 10.1002/anie.199500801

Formal Oxidation State versus Partial Charge—A Comment
journal, May 1995

  • Kaupp, Martin; von Schnering, Hans Georg
  • Angewandte Chemie International Edition in English, Vol. 34, Issue 9
  • DOI: 10.1002/anie.199509861

A Bonding Quandary-or-A Demonstration of the Fact That Scientists Are Not Born With Logic
journal, August 2009

  • Alvarez, Santiago; Hoffmann, Roald; Mealli, Carlo
  • Chemistry - A European Journal, Vol. 15, Issue 34
  • DOI: 10.1002/chem.200900239

Spectroscopic Evidence for a 3d 10 Ground State Electronic Configuration and Ligand Field Inversion in [Cu(CF 3 ) 4 ] 1–
journal, February 2016

  • Walroth, Richard C.; Lukens, James T.; MacMillan, Samantha N.
  • Journal of the American Chemical Society, Vol. 138, Issue 6
  • DOI: 10.1021/jacs.5b10819

Experimental X-ray Electron Density Study of Atomic Charges, Oxidation States, and Inverted Ligand Field in Cu(CF 3 ) 4
journal, January 2019


The Myth of d 8 Copper(III)
journal, October 2019

  • DiMucci, Ida M.; Lukens, James T.; Chatterjee, Sudipta
  • Journal of the American Chemical Society, Vol. 141, Issue 46
  • DOI: 10.1021/jacs.9b09016

Ligand-dependent formation of ion-pair Cu I /Cu III trifluoromethyl complexes containing bisphosphines
journal, January 2016

  • Zhang, Song-Lin; Bie, Wen-Feng
  • Dalton Transactions, Vol. 45, Issue 44
  • DOI: 10.1039/C6DT03016E

M−C Bond Homolysis in Coinage‐Metal [M(CF 3 ) 4 ] Derivatives
journal, June 2019

  • Baya, Miguel; Joven‐Sancho, Daniel; Alonso, Pablo J.
  • Angewandte Chemie, Vol. 131, Issue 29
  • DOI: 10.1002/ange.201903496

Silver-Catalyzed Decarboxylative Trifluoromethylation of Aliphatic Carboxylic Acids
journal, August 2017

  • Tan, Xinqiang; Liu, Zhonglin; Shen, Haigen
  • Journal of the American Chemical Society, Vol. 139, Issue 36
  • DOI: 10.1021/jacs.7b07944

Copper‐Mediated Trifluoromethylation of Benzylic Csp 3 −H Bonds
journal, July 2018

  • Paeth, Matthew; Carson, William; Luo, Jheng‐Hua
  • Chemistry – A European Journal, Vol. 24, Issue 45
  • DOI: 10.1002/chem.201802766

1,2‐(Bis)trifluoromethylation of Alkynes: A One‐Step Reaction to Install an Underutilized Functional Group
journal, July 2019

  • Guo, Shuo; AbuSalim, Deyaa I.; Cook, Silas P.
  • Angewandte Chemie International Edition, Vol. 58, Issue 34
  • DOI: 10.1002/anie.201905247

Aqueous Benzylic C–H Trifluoromethylation for Late-Stage Functionalization
journal, September 2018

  • Guo, Shuo; AbuSalim, Deyaa I.; Cook, Silas P.
  • Journal of the American Chemical Society, Vol. 140, Issue 39
  • DOI: 10.1021/jacs.8b08547

Accessing perfluoroalkyl nickel( ii ), ( iii ), and ( iv ) complexes bearing a readily attached [C 4 F 8 ] ligand
journal, January 2015

  • Yu, S.; Dudkina, Y.; Wang, H.
  • Dalton Transactions, Vol. 44, Issue 45
  • DOI: 10.1039/C5DT01771H

Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes
journal, February 2015


Oxidatively Induced C–H Activation at High Valent Nickel
journal, April 2017

  • Chong, Eugene; Kampf, Jeff W.; Ariafard, Alireza
  • Journal of the American Chemical Society, Vol. 139, Issue 17
  • DOI: 10.1021/jacs.7b02387

Connecting Organometallic Ni(III) and Ni(IV): Reactions of Carbon-Centered Radicals with High-Valent Organonickel Complexes
journal, May 2019

  • Bour, James R.; Ferguson, Devin M.; McClain, Edward J.
  • Journal of the American Chemical Society, Vol. 141, Issue 22
  • DOI: 10.1021/jacs.9b02411

C−H Bond Trifluoromethylation of Arenes Enabled by a Robust, High-Valent Nickel(IV) Complex
journal, September 2017

  • D'Accriscio, Florian; Borja, Pilar; Saffon-Merceron, Nathalie
  • Angewandte Chemie International Edition, Vol. 56, Issue 42
  • DOI: 10.1002/anie.201706237

A Five-Coordinate Nickel(II) Fluoroalkyl Complex as a Precursor to a Spectroscopically Detectable Ni(III) Species
journal, May 2013

  • Zhang, Cheng-Pan; Wang, Huan; Klein, Axel
  • Journal of the American Chemical Society, Vol. 135, Issue 22
  • DOI: 10.1021/ja4030462

Electronic Structure of Tetracyanonickelate(II)
journal, November 2019


Charge-Transfer and Ligand-Field Spectra of Tetrahedral Tetrahalonickel(II) Ions in Molten Dimethyl Sulfone and Molten Organic Halide Salts
journal, November 1964

  • Smith, G. Pedro.; Liu, C. H.; Griffiths, Trevor R.
  • Journal of the American Chemical Society, Vol. 86, Issue 22
  • DOI: 10.1021/ja01076a014

Probing the Electron Accepting Orbitals of Ni-Centered Hydrogen Evolution Catalysts with Noninnocent Ligands by Ni L-Edge and S K-Edge X-ray Absorption
journal, October 2018


Determination of absorption coefficients for concentrated samples by fluorescence detection
journal, June 1993


Undistorted X-ray Absorption Spectroscopy Using s-Core-Orbital Emissions
journal, April 2016

  • Golnak, Ronny; Xiao, Jie; Atak, Kaan
  • The Journal of Physical Chemistry A, Vol. 120, Issue 18
  • DOI: 10.1021/acs.jpca.6b01699

Sulfur K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand−Metal Bond Covalency:  Metal vs Ligand Oxidation in Copper and Nickel Dithiolene Complexes
journal, February 2007

  • Sarangi, Ritimukta; DeBeer George, Serena; Rudd, Deanne Jackson
  • Journal of the American Chemical Society, Vol. 129, Issue 8
  • DOI: 10.1021/ja0665949

Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds
journal, January 2005

  • Solomon, Edward I.; Hedman, Britt; Hodgson, Keith O.
  • Coordination Chemistry Reviews, Vol. 249, Issue 1-2
  • DOI: 10.1016/j.ccr.2004.03.020

Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory
journal, December 2008

  • DeBeer George, Serena; Petrenko, Taras; Neese, Frank
  • The Journal of Physical Chemistry A, Vol. 112, Issue 50
  • DOI: 10.1021/jp803174m

A spectroscopy oriented configuration interaction procedure
journal, November 2003

  • Neese, Frank
  • The Journal of Chemical Physics, Vol. 119, Issue 18
  • DOI: 10.1063/1.1615956

Disproportionation among aryloxyphosphoranes
journal, August 1979

  • Sigal, Irving S.; Westheimer, F. H.
  • Journal of the American Chemical Society, Vol. 101, Issue 18
  • DOI: 10.1021/ja00512a036

Studies of copper(I) olefin complexes. Formation constants of copper olefin complexes with 2,2'-bipyridine, 1,10-phenanthroline, and their derivatives
journal, July 1986

  • Munakata, Megumu; Kitagawa, Susumu; Kosome, Shigeru
  • Inorganic Chemistry, Vol. 25, Issue 15
  • DOI: 10.1021/ic00235a027

Copper(I) and silver(I) carbonyls. To be or not to be nonclassical
journal, January 2000

  • Strauss, Steven H.
  • Journal of the Chemical Society, Dalton Transactions, Issue 1
  • DOI: 10.1039/a908459b