Breaking bonds and breaking rules: inert-bond activation by [(iPr3P)Ni]5H4 and catalytic stereospecific norbornene dimerization

Junyang Liu; Manar M. Shoshani; Kethya Sum; Samuel A. Johnson

doi:10.1039/D2CC06681E

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Breaking bonds and breaking rules: inert-bond activation by [(ⁱPr₃P)Ni]₅H₄ and catalytic stereospecific norbornene dimerization†

Junyang Liu,

^a Manar M. Shoshani,

‡^a Kethya Sum^a and Samuel A. Johnson

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry and Biochemistry, University of Windsor, Sunset Avenue 401, Windsor, ON, Canada
E-mail: sjohnson@uwindsor.ca
Fax: (+1) 519-973-7098

Abstract

The facile carbon atom abstraction reaction by [(ⁱPr₃P)Ni]₅H₆ (1) with various terminal alkenes to give [(ⁱPr₃P)Ni]₅H₄(μ₅-C) (2) occurs via a common highly reactive intermediate [(ⁱPr₃P)Ni]₅H₄ (3), which was isolated by the reaction of 1 with norbornene. Temperature dependent ¹H and ³¹P{¹H} NMR chemical shifts of 3 are consistent with a thermally populated triplet excited state only 2 kcal mol⁻¹ higher energy than the diamagnetic ground state. Complex 3 catalyzes the dimerization of norbornene to stereoselectively provide exclusively (Z) anti-(bis-2,2'-norbornylidene).

This article is part of the themed collection: Chemical Communications HOT Articles 2023

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Article information

DOI: https://doi.org/10.1039/D2CC06681E
Article type: Communication
Submitted: 07 Dec 2022
Accepted: 13 Jan 2023
First published: 23 Jan 2023

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Chem. Commun., 2023,59, 3542-3545

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Breaking bonds and breaking rules: inert-bond activation by [(ⁱPr₃P)Ni]₅H₄ and catalytic stereospecific norbornene dimerization

J. Liu, M. M. Shoshani, K. Sum and S. A. Johnson, Chem. Commun., 2023, 59, 3542 DOI: 10.1039/D2CC06681E

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