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A Ketimide-Stabilized Palladium Nanocluster with a Hexagonal Aromatic Pd Core.

Author(s) Cook, A.W.; Hrobárik, P.; Damon, P.L.; Wu, G.; Hayton, T.W.
Journal Inorg Chem
Date Published 2020 Jan 21
Abstract

Herein, we report the synthesis and characterization of the mixed-valent, ketimide-stabilized Pd nanosheet, [Pd(N═CBu)] (), via reaction of PdCl(PhCN) and Li(N═CBu). BuCN, isobutylene, and isobutane are also formed in the reaction. The presence of these products suggests that Li(N═CBu) acts as a reducing agent in the transformation, converting the Pd(II) starting material into the mixed-valent Pd(I)/Pd(0) product. Complex features a hexagonal planar [Pd] core stabilized by six ketimide ligands, which surround the [Pd] center in an alternating up/down fashion. NMR spectroscopic studies, as well as density functional theory (DFT) calculations, suggest that is formed via the intermediacy of the bimetallic Pd(II) ketimide complex, [(BuC═N)Pd(μ-N,C-═C(Bu)C(Me)H)Pd(N═CBu)] (). DFT calculations also reveal that is a rare example of an all-metal aromatic nanocluster with hexagonal symmetry, sustaining a net diatropic ring-current of 10.6 nA/T, which is similar to that of benzene (11.8 nA/T) or other well-established transition-metal aromatic systems. Finally, we have found that reacts with PhP, cleanly forming the tris-ligated 16-electron Pd(0) phosphine complex, Pd(PPh) (), suggesting that could be a useful precatalyst for a variety of cross-coupling reactions.

DOI 10.1021/acs.inorgchem.9b03276
ISSN 1520-510X
Citation Cook AW, Hrobárik P, Damon PL, Wu G, Hayton TW. A Ketimide-Stabilized Palladium Nanocluster with a Hexagonal Aromatic Pd Core. Inorg Chem. 2020;59(2):1471-1480.

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