Carbon−Carbon Bond-Forming Reductive Elimination from

Isolated
Nickel(III) Complexes
-Muhsin Abdul Majeed(IMS17148)

SUMMARY
The ability of Ni to undergo single electron redox events facilitates it as a catalyst distinct from
conventionally used Pd. Majority of work on the organometallic chemistry of NiIII has focused on
complexes bearing a single aryl or alkyl donor ligand. And many of these had been isolated and their
reactivity with heteroatom and carbon nucleophiles had been studied. But examples of more catalytically
relevant diorganonickel(III) complexes have remained elusive until very recently. Kochi showed that
transient [NiIII(R)(R1)] intermediates were present in Ni-mediated C(sp2)−C(sp2) coupling reactions but
these intermediates were only inferred from reactivity studies and low temperature cyclic voltammetry
and were not directly observed or structurally characterized. Recently, Mirica demonstrated that a
tetradentate nitrogen donor ligand can be used to support a detectable NiIII(CH3) (aryl) intermediate.
However, on warming from −50 °C to room temperature, it underwent C(sp2)−C(sp3) bond-forming
reductive elimination. Later she used a tetradentate ligand scaffold to generate an isolable NiIII dimethyl
complex that undergoes ethane reductive elimination over 12 h in MeCN at room temperature. So,
working on all these a project was developed to synthesize isolable Ni(III) complexes of general structure
LnNi(III)(R)(R1).
Facial tridentate tris(pyrazolyl)borate ligand was taken to support a variety of isolable Ni(III) complexes.
And carbon donor ligands (R and R1) that are deactivated toward C−C bond forming reductive elimination
were chosen as precursors(1a-f).

Initially, 1e− oxidation of TpNi(II) complexes 1a−f was evaluated using cyclic voltammetry (CV) and
expected that complexes exhibiting quasi-reversible 1e− oxidations by CV were to form stable NiIII
complexes upon chemical oxidation. Compounds 1a−c and 1e showed quasi-reversible 1e−oxidative
waves. But, 1d and 1f exhibited irreversible 1e− oxidations. Also, 1a−c and 1e all exhibit a large peak-to
peak separation for the NiII/III couple and was interpreted to be due to 1e− electrochemical oxidation of
Ni(II) to Ni(III) triggers a change in the Tp binding mode from κ2 to κ3. Then, using FcBF4 as oxidizing
agent in MeCN at −35 °C resulted in the rapid disappearance of the diamagnetic 1H and 19F NMR
signals of the Ni(II) starting materials. The in situ analysis of the reactions of 2a−c and 2e by EPR
spectroscopy showed signals consistent with the formation of a S = 1/2 Ni(III) intermediate. In contrast,
the oxidations of 1d and 1f did not show detectable Ni(III) products, as determined by EPR spectroscopy.
Instead, products derived from C−C coupling were detected by 1H and 19F NMR spectroscopy.
For isolating Ni(III) complexes(2a-c and e) AgBF4 was used as oxidant as it generates insoluble Ag 0 as
byproduct which is insoluble. Then, the products formed were taken for EPR spectroscopy and the
spectra of 2a-c and e exhibited hyperfine coupling with one(2a and 2b) or two(2c and 2e) N atom and this
difference in coupling is seen due to acetonitrile ligands in the latter forming octahedral complex(2c and
2e-MeCN). Further, X-ray crystallography was done and was seen that Tp ligand binds in a κ3-fashion.
The solid-state structures of 2a, 2b, and 2e exhibit a slightly distorted square pyramidal geometry, while
2c is octahedral, with a molecule of MeCN occupying the sixth coordination site. But as inferred from
EPR, 2e-MeCN adduct wasn’t seen with X-ray.

Reactivity of complexes are as follows:

In order to study the mechanism of the reaction Ph-CF3 coupling of 2e was examined. Here 3 mechanism
were possible:

Now to check the validity of each pathways-

 Pathway (a)-Firstly, presence of Ni(IV) complex 4 was checked under milder conditions through
19F NMR spectroscopy and showed no presence. Also, radical trapping experiments were done:
 Collectively, these results showed the inconsistency of mechanism (a) or any other mechanism
involving F3C• intermediates.

 Pathway (c)- reactivity of the cationic Ni(IV) complex 5, which would be the key intermediate in
this disproportionation mechanism. So, to check this the following reaction was done:

While attempts to isolate this compound were unsuccessful, these data are consistent with the
formation of Ni(IV) complex 5, which undergoes subsequent Ph−CF3 reductive elimination.
Also, redox disproportionation would involve the formation of 0.5 equiv of the starting NiII complex
1e, which is expected to be stable and observable by NMR spectroscopy under the reaction
conditions. However, 1e was not detected by 1H or 19F NMR. Further, disproportionation
reactions exhibit second order dependence on [Ni] which checked under 19F NMR spectroscopy
for different concentrations of [Ni] showed order to be 0.8. All these details were against redox
disproportionation reaction.

Thus, it was plausible that reductive elimination from Ni(III) complex 2e as the most likely mechanism for
Ph−CF3 coupling.

Furthermore, it was seen that the yield/mass balance of this reaction can be enhanced through the
addition of a weak oxidant, which is believed to quench Ni(I) byproducts and thereby minimize undesired
side reactions.