2016OrganometallicsRequires access

An Organometalllic NiIV Complex That Participates in Competing Transmetalation and C(sp2)–O Bond-Forming Reductive Elimination Reactions

Elizabeth A. Meucci, Nicole M. Camasso, Melanie S. Sanford

Open publisher page 41 citations

Abstract

This communication describes the synthesis of an organometallic Ni IV complex bearing a labile trifluoroacetate (OTFA) ligand via the oxidation of a Ni II precursor with PhI(OTFA) 2 . Intramolecular C(sp 2 )–O bond-forming reductive elimination from this Ni IV complex is relatively slow, requiring 6 h at 70 °C to reach completion. In contrast, transmetalation with TMSCF 3 occurs within just 1 h at room temperature to generate a Ni IV –CF 3 complex. These studies show that intermolecular reactions such as transmetalation can be competitive with intramolecular reductive elimination processes at Ni IV centers.

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What this paper is about

This communication describes the synthesis of an organometallic Ni IV complex bearing a labile trifluoroacetate (OTFA) ligand via the oxidation of a Ni II precursor with PhI(OTFA) 2 . Intramolecular C(sp 2 )–O bond-forming reductive elimination from this Ni IV complex is relatively slow, requiring 6 h at 70 °C to reach completion. In contrast, transmetalation with TMSCF 3 occurs within just 1 h at room temperature to generate a Ni IV –CF 3 complex. These studies show that intermolecular reactions such as transmetalation can be competitive with intramolecular reductive elimination processes at Ni IV centers.

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OpenAlex reports 41 citations for this work. Citation counts describe recorded attention and do not establish research quality.

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Available abstract

This communication describes the synthesis of an organometallic Ni IV complex bearing a labile trifluoroacetate (OTFA) ligand via the oxidation of a Ni II precursor with PhI(OTFA) 2 . Intramolecular C(sp 2 )–O bond-forming reductive elimination from this Ni IV complex is relatively slow, requiring 6 h at 70 °C to reach completion. In contrast, transmetalation with TMSCF 3 occurs within just 1 h at room temperature to generate a Ni IV –CF 3 complex. These studies show that intermolecular reactions such as transmetalation can be competitive with intramolecular reductive elimination processes at Ni IV centers.

Key concepts: Transmetalation, Reductive elimination, Chemistry, Intramolecular force, Ligand (biochemistry), Intermolecular force, Oxidative addition, Medicinal chemistry

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