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Reductively Stable Hydrogen-Bonding Ligands Featuring Appended CF₂-H Units.

ABSTRACT: We present the development of ligands featuring the unconventional hydrogen bond donor, -CF₂H, within a metal's secondary coordination sphere. When metalated with palladium, o-CF₂H-functionalized 1,10-phenanthroline provides highly directed H-bonding interactions with Pd-coordinated substrates. Spectroscopic and computational analyses with a series of X-type ligand acceptors (-F, -Cl, -Br, -OR) establish the H-bonding interaction strength for the -CF₂H group (∼3 kcal/mol). The synthesis of Pd⁰/Ni⁰ complexes and subsequent coupling (Ni) highlight the unique reductive and base compatibility of the -CF₂H hydrogen bond donor group.

SUBMITTER: Shanahan JP

PROVIDER: S-EPMC8640959 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Reductively Stable Hydrogen-Bonding Ligands Featuring Appended CF2-H Units.

Shanahan James P JP Mullis Danielle M DM Zeller Matthias M Szymczak Nathaniel K NK

Journal of the American Chemical Society 20200430 19

We present the development of ligands featuring the unconventional hydrogen bond donor, -CF2H, within a metal's secondary coordination sphere. When metalated with palladium, o-CF2H-functionalized 1,10-phenanthroline provides highly directed H-bonding interactions with Pd-coordinated substrates. Spectroscopic and computational analyses with a series of X-type ligand acceptors (-F, -Cl, -Br, -OR) establish the H-bonding interaction strength for the -CF2</su ...[more]

PMID: 32352797

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