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Published September 1, 2020 | public
Journal Article

A Hemilabile Diphosphine Pyridine Pincer Ligand: σ- and π-Binding in Molybdenum Coordination Complexes

Abstract

A series of molybdenum compounds supported by a hemilabile pyridine diphosphine pincer ligand have been synthesized. The ligand demonstrates variable binding modes, adapting to the electronic and geometric requirements of the metal center. In Mo⁰ and Mo^(II) polycarbonyl complexes, coordination through the σ-donating pyridine nitrogen lone pair is observed. Upon oxidative group transfer with anionic azide, a Mo^(IV) nitride compound is formed, accompanied by a change in the ancillary ligand binding mode to the pyridine π-system. The σ-coordination was restored by subsequent functionalization of the nitride moiety with either silyl electrophiles or protons. Protonation results in redox disproportionation with concomitant nitride functionalization. Characterization by single crystal X-ray diffraction, nuclear magnetic resonance, and infrared spectroscopy is discussed.

Additional Information

© 2020 Published by Elsevier Ltd. Received 5 February 2020, Revised 28 May 2020, Accepted 29 May 2020, Available online 4 June 2020. Dedicated to John Bercaw on the occasion of his 75th birthday. Thank you, John, for your inspiring science, mentorship, and friendship!

Additional details

Created:
August 22, 2023
Modified:
October 20, 2023