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. 2022 Apr 11;13(18):5171-5175.
doi: 10.1039/d2sc00960a. eCollection 2022 May 11.

[Ni30S16(PEt3)11]: an open-shell nickel sulfide nanocluster with a "metal-like" core

Alexander J Touchton  1 , Guang Wu  1 , Trevor W Hayton  1
Affiliations

[Ni30S16(PEt3)11]: an open-shell nickel sulfide nanocluster with a "metal-like" core

Alexander J Touchton et al. Chem Sci. .

Abstract

Reaction of [Ni(1,5-cod)2] (30 equiv.) with PEt3 (46 equiv.) and S8 (1.9 equiv.) in toluene, followed by heating at 115 °C for 16 h, results in the formation of the atomically precise nanocluster (APNC), [Ni30S16(PEt3)11] (1), in 14% isolated yield. Complex 1 represents the largest open-shell Ni APNC yet isolated. In the solid state, 1 features a compact "metal-like" core indicative of a high degree of Ni-Ni bonding. Additionally, SQUID magnetometry suggests that 1 possesses a manifold of closely-spaced electronic states near the HOMO-LUMO gap. In situ monitoring by ESI-MS and 31P{1H} NMR spectroscopy reveal that 1 forms via the intermediacy of smaller APNCs, including [Ni8S5(PEt3)7] and [Ni26S14(PEt3)10] (2). The latter APNC was also characterized by X-ray crystallography and features a nearly identical core structure to that found in 1. This work demonstrates that large APNCs with a high degree of metal-metal bonding are isolable for nickel, and not just the noble metals.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Solid-state structure of [Ni30S16(PEt3)11]·Et2O (1·Et2O) from two different orientations. (A and B) Ni21 core. (C and D) The three [cyclo-{Ni(μ-S)}3] units attached to the Ni21S7 core. (E and F) Ni-only structure of 1. (G and H) Full molecular structure. Color scheme: Nishell, green; Nicore, blue; S, yellow; P, orange; C, grey. Carbon atoms are shown in wireframe. Diethyl ether solvate molecule and hydrogen atoms were omitted for clarity.
Fig. 2
Fig. 2. Characterization data for 1. (A) Partial 31P{1H} NMR spectrum of 1 in toluene-d8. (B) A plot of 31P{1H} NMR chemical shift versus T−1 for the 30 ppm (25 °C) resonance. (C) Variable temperature magnetic susceptibility (χT) for 1 collected at 10 000 Oe. (D) Partial ESI-MS mass spectrum of 1 in THF (capillary voltage of 2.50 kV, positive ion mode) showing a peak at 3572.43 m/z assignable to [Ni30S16(PEt3)11]+ (calcd 3572.57 m/z).
Fig. 3
Fig. 3. Solid-state structure of [Ni26S14(PEt3)10]·C5H12 (2·C5H12) from two different orientations. (A and B) Ni20S core. (C and D) The two [cyclo-{Ni(μ-S)}3] units attached to the Ni20S8 core. (E and F) Ni-only structure of 2. (G and H) Full molecular structure. Color scheme: Nishell, green; Nicore, blue; S, yellow; P, orange; C, grey. Carbon atoms are shown in wireframe. Pentane solvate molecule and hydrogen atoms were omitted for clarity.
See this image and copyright information in PMC

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