A Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration.

TitleA Proton-Switchable Bifunctional Ruthenium Complex That Catalyzes Nitrile Hydroboration.
Publication TypeJournal Article
Year of Publication2015
AuthorsGeri JB, Szymczak NK
JournalJ Am Chem Soc
Volume137
Issue40
Pagination12808-14
Date Published2015 Oct 14
ISSN1520-5126
KeywordsBoron, Catalysis, Crystallography, X-Ray, Nitriles, Protons, Ruthenium
Abstract

A new bifunctional pincer ligand framework bearing pendent proton-responsive hydroxyl groups was prepared and metalated with Ru(II) and subsequently isolated in four discrete protonation states. Stoichiometric reactions with H2 and HBPin showed facile E-H (E = H or BPin) activation across a Ru(II)-O bond, providing access to unusual Ru-H species with strong interactions with neighboring proton and boron atoms. These complexes were found to promote the catalytic hydroboration of ketones and nitriles under mild conditions, and the activity was highly dependent on the ligand's protonation state. Mechanistic experiments revealed a crucial role of the pendent hydroxyl groups for catalytic activity.

DOI10.1021/jacs.5b08406
Alternate JournalJ Am Chem Soc
PubMed ID26425797