Issue 12, 2023

From M6 to M12, M19 and M38 molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

Abstract

Heterometallic Chini-type clusters [Pt6−xNix(CO)12]2− (x = 0–6) were obtained by reactions of [Pt6(CO)12]2− with Ni-clusters such as [Ni6(CO)12]2−, [Ni9(CO)18]2− and [H2Ni12(CO)21]2−, or from [Pt9(CO)18]2− and [Ni6(CO)12]2−. The Pt/Ni composition of [Pt6−xNix(CO)12]2− (x = 0–6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt9(CO)18]2− with [Ni9(CO)18]2− and [H2Ni12(CO)21]2−, as well as reactions of [Pt12(CO)24]2− with [Ni6(CO)12]2−, [Ni9(CO)18]2− and [H2Ni12(CO)21]2−, afforded [Pt9−xNix(CO)18]2− (x = 0–9) species. [Pt6−xNix(CO)12]2− (x = 1–5) were converted into [Pt12−xNix(CO)21]4− (x = 2–10) upon heating in CH3CN at 80 °C, with almost complete retention of the Pt/Ni composition. Reaction of [Pt12−xNix(CO)21]4− (x ≈ 8) with HBF4·Et2O afforded the [HPt14+xNi24−x(CO)44]5− (x ≈ 0.7) nanocluster. Finally, [Pt19−xNix(CO)22]4− (x = 2–6) could be obtained by heating [Pt9−xNix(CO)18]2− (x = 1–3) in CH3CN at 80 °C, or [Pt6−xNix(CO)12]2− (2–4) in DMSO at 130 °C. The molecular structures of these new alloy nanoclusters have been determined by single crystal X-ray diffraction. The site preference of Pt and Ni within their metal cages has been computationally investigated. The electrochemical and IR spectroelectrochemical behavior of [Pt19−xNix(CO)22]4− (x = 3.11) has been studied and compared to the isostructural homometallic nanocluster [Pt19(CO)22]4−.

Graphical abstract: From M6 to M12, M19 and M38 molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

Supplementary files

Article information

Article type
Paper
Submitted
09 Nov 2022
Accepted
27 Feb 2023
First published
28 Feb 2023
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2023,52, 3623-3642

From M6 to M12, M19 and M38 molecular alloy Pt–Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

C. Cesari, B. Berti, M. Bortoluzzi, C. Femoni, T. Funaioli, F. M. Vivaldi, M. C. Iapalucci and S. Zacchini, Dalton Trans., 2023, 52, 3623 DOI: 10.1039/D2DT03607J

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