A d10 Ni–(H2) Adduct as an Intermediate in HH Oxidative Addition across a NiB Bond1. (9th December 2013)

• Record Type: Journal Article
• Authors: Harman, W. Hill; Lin, Tzu‐Pin; Peters, Jonas C.
• Is Part Of: Angewandte Chemie. Volume 126:Number 4(2014)
• Page Start: 1099
• Page End: 1104
• Publication Date: 2013-12-09
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201308175
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Bifunctional EH activation offers a promising approach for the design of two‐electron‐reduction catalysts with late first‐row metals, such as Ni. To this end, we have been pursuing H₂ activation reactions at late‐metal boratranes and herein describe a diphosphine–borane‐supported Ni—(H₂) complex, [(^PhDPB^{<italic>i</italic>Pr})Ni(H₂)], which has been characterized in solution. ¹H NMR spectroscopy confirms the presence of an intact H₂ ligand. A range of data, including electronic‐structure calculations, suggests a d¹⁰ configuration for [(^PhDPB^{<italic>i</italic>Pr})Ni(H₂)] as most appropriate. Such a configuration is highly unusual among transition‐metal H₂ adducts. The nonclassical H₂ adduct is an intermediate in the complete activation of H₂ across the NiB interaction. Reaction‐coordinate analysis suggests synergistic activation of the H₂ ligand by both the Ni and B centers of the nickel boratrane subunit, thus highlighting an important role of the borane ligand both in stabilizing the d¹⁰ Ni—(H₂) interaction and in the H—H cleavage step.</p> </abstract>