From M 6 to M 12 , M 19 and M 38 molecular alloy Pt-Ni carbonyl nanoclusters: selective growth of atomically precise heterometallic nanoclusters

• Published in: Dalton transactions : an international journal of inorganic chemistry 2023-03, Vol.52 (12), p.3623-3642
• Main Authors: Cesari, Cristiana, Berti, Beatrice, Bortoluzzi, Marco, Femoni, Cristina, Funaioli, Tiziana, Vivaldi, Federico Maria, Iapalucci, Maria Carmela, Zacchini, Stefano
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/D2DT03607J

Heterometallic Chini-type clusters [Pt Ni (CO) ] ( = 0-6) were obtained by reactions of [Pt (CO) ] with Ni-clusters such as [Ni (CO) ] , [Ni (CO) ] and [H Ni (CO) ] , or from [Pt (CO) ] and [Ni (CO) ] . The Pt/Ni composition of [Pt Ni (CO) ] ( = 0-6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt (CO) ] with [Ni (CO) ] and [H Ni (CO) ] , as well as reactions of [Pt (CO) ] with [Ni (CO) ] , [Ni (CO) ] and [H Ni (CO) ] , afforded [Pt Ni (CO) ] ( = 0-9) species. [Pt Ni (CO) ] ( = 1-5) were converted into [Pt Ni (CO) ] ( = 2-10) upon heating in CH CN at 80 °C, with almost complete retention of the Pt/Ni composition. Reaction of [Pt Ni (CO) ] ( ≈ 8) with HBF ·Et O afforded the [HPt Ni (CO) ] ( ≈ 0.7) nanocluster. Finally, [Pt Ni (CO) ] ( = 2-6) could be obtained by heating [Pt Ni (CO) ] ( = 1-3) in CH CN at 80 °C, or [Pt Ni (CO) ] (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 [Pt Ni (CO) ] ( = 3.11) has been studied and compared to the isostructural homometallic nanocluster [Pt (CO) ] .