Amplifying Reactivity of Metal Hydrides: A Heterotrimetallic NiAl2(mu(2)-H)(2) Catalyst for the Dearomatization of N-Heterocycles

• Published in: Organometallics Vol. 42; no. 6; pp. 435 - 440
• Main Authors: De Leon, Edgardo, Gonzalez, Fernando, Bauskar, Preetika, Gonzalez-Eymard, Sergio, Santos, David De Los, Shoshani, Manar M.
• Format: Journal Article
• Language: English
• Published: WASHINGTON Amer Chemical Soc 27.03.2023
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Physical Sciences; Science & Technology; H BOND ACTIVATION; HYDROBORATION; HYDROGENATION; NICKEL; COMPLEXES; LIGAND; CLEAVAGE; C-H; BORYL; COBALT
• DOI: 10.1021/acs.organomet.2c00668
• ISSN: 0276-7333

Identifying methods to modulate the reactivity of metal hydrides is lacking yet highly desirable given the role they play in a plethora of catalytic applications. Herein we report novel methodology to amplify the reactivity of metal hydrides through the design of well-defined heterometallic bridged hydride species. Catalytic hydroboration of quinolines was dramatically altered by the addition of a secondary metal to bridge the Al-hydride species LAlH. Specifically, the addition of Ni(COD)(2) led to the formation of novel heterotrimetallic species 1 which features Ni participating in 3-center bonding with sterically accessible Al-H species and exhibits catalytic hydroboration of sterically encumbered quinolines and approximately a 400 times enhancement in catalytic reactivity in comparison to LAlH.