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?-Noninnocence: Masked Phenyl-Cation Transfer at Formal NiIV.

ABSTRACT: Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of -2 at a transition-metal center. For a series of formal high-valent NiIV complexes, aryl-CF3 bond-forming reductive elimination was reported to occur readily (Bour et?al. J. Am. Chem. Soc. 2015, 137, 8034-8037). We report a computational analysis of this reaction and find that, unexpectedly, the formal NiIV centers are better described as approaching a +II oxidation state, originating from highly covalent metal-ligand bonds, a phenomenon attributable to ?-noninnocence. A direct consequence is that the elimination of aryl-CF3 products occurs in an essentially redox-neutral fashion, as opposed to a reductive elimination. This is supported by an electron flow analysis which shows that an anionic CF3 group is transferred to an electrophilic aryl group. The uncovered role of ?-noninnocence in metal-ligand bonding, and of an essentially redox-neutral elimination as an elementary organometallic reaction step, may constitute concepts of broad relevance to organometallic chemistry.

SUBMITTER: Steen JS 

PROVIDER: S-EPMC6771483 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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σ-Noninnocence: Masked Phenyl-Cation Transfer at Formal Ni<sup>IV</sup>.

Steen Jelte S JS   Knizia Gerald G   Klein Johannes E M N JEMN  

Angewandte Chemie (International ed. in English) 20190715 37

Reductive elimination is an elementary organometallic reaction step involving a formal oxidation state change of -2 at a transition-metal center. For a series of formal high-valent Ni<sup>IV</sup> complexes, aryl-CF<sub>3</sub> bond-forming reductive elimination was reported to occur readily (Bour et al. J. Am. Chem. Soc. 2015, 137, 8034-8037). We report a computational analysis of this reaction and find that, unexpectedly, the formal Ni<sup>IV</sup> centers are better described as approaching a  ...[more]

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