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

Wan, Ruomeng and Buss, Joshua A. and Horak, Kyle T. and Agapie, Theodor (2020) A Hemilabile Diphosphine Pyridine Pincer Ligand: σ- and π-Binding in Molybdenum Coordination Complexes. Polyhedron, 187 . Art. No. 114631. ISSN 0277-5387. https://resolver.caltech.edu/CaltechAUTHORS:20200604-123156381

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1016/j.poly.2020.114631DOIArticle
ORCID:
AuthorORCID
Buss, Joshua A.0000-0002-3347-8583
Agapie, Theodor0000-0002-9692-7614
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!
Subject Keywords:Hemilabile Ligands; Pincer Complexes; Molybdenum; Transition Metal Nitride
Record Number:CaltechAUTHORS:20200604-123156381
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200604-123156381
Official Citation:Ruomeng Wan, Joshua A. Buss, Kyle T. Horak, Theodor Agapie, A hemilabile diphosphine pyridine pincer ligand: σ- and π-binding in molybdenum coordination complexes, Polyhedron, Volume 187, 2020, 114631, ISSN 0277-5387, https://doi.org/10.1016/j.poly.2020.114631. (http://www.sciencedirect.com/science/article/pii/S0277538720302886)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:103694
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:04 Jun 2020 20:16
Last Modified:02 Jul 2020 17:37

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