Dipartimento di Chimica Industriale "Toso Montanari", Università di Bologna, Viale Risorgimento 4, 40136 Bologna, Italy.
Dipartimento di Scienze Molecolari e Nanosistemi, Ca' Foscari University of Venice, Via Torino 155, 30175 Mestre (Ve), Italy.
Dalton Trans. 2023 Mar 21;52(12):3623-3642. doi: 10.1039/d2dt03607j.
Heterometallic Chini-type clusters [PtNi(CO)] ( = 0-6) were obtained by reactions of [Pt(CO)] with Ni-clusters such as [Ni(CO)], [Ni(CO)] and [HNi(CO)], or from [Pt(CO)] and [Ni(CO)]. The Pt/Ni composition of [PtNi(CO)] ( = 0-6) depended on the nature of the reagents employed and their stoichiometry. Reactions of [Pt(CO)] with [Ni(CO)] and [HNi(CO)], as well as reactions of [Pt(CO)] with [Ni(CO)], [Ni(CO)] and [HNi(CO)], afforded [PtNi(CO)] ( = 0-9) species. [PtNi(CO)] ( = 1-5) were converted into [PtNi(CO)] ( = 2-10) upon heating in CHCN at 80 °C, with almost complete retention of the Pt/Ni composition. Reaction of [PtNi(CO)] ( ≈ 8) with HBF·EtO afforded the [HPtNi(CO)] ( ≈ 0.7) nanocluster. Finally, [PtNi(CO)] ( = 2-6) could be obtained by heating [PtNi(CO)] ( = 1-3) in CHCN at 80 °C, or [PtNi(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 [PtNi(CO)] ( = 3.11) has been studied and compared to the isostructural homometallic nanocluster [Pt(CO)].
异核奇尼型簇合物[PtNi(CO)]（ = 0-6）是通过[Pt(CO)]与 Ni 簇合物如[Ni(CO)]、[Ni(CO)]和[HNi(CO)]的反应，或者通过[Pt(CO)]与[Ni(CO)]的反应得到的。[PtNi(CO)]（ = 0-6）的 Pt/Ni 组成取决于所使用的试剂的性质及其化学计量比。[Pt(CO)]与[Ni(CO)]和[HNi(CO)]的反应，以及[Pt(CO)]与[Ni(CO)]、[Ni(CO)]和[HNi(CO)]的反应，得到了[PtNi(CO)]（ = 0-9）物种。在 CHCN 中于 80°C 加热时，[PtNi(CO)]（ = 1-5）转化为[PtNi(CO)]（ = 2-10），几乎完全保留了 Pt/Ni 的组成。[PtNi(CO)]（ ≈ 8）与 HBF·EtO 的反应得到了[HPtNi(CO)]（ ≈ 0.7）纳米簇。最后，通过在 80°C 的 CHCN 中加热[PtNi(CO)]（ = 1-3）或在 130°C 的 DMSO 中加热[PtNi(CO)]（2-4），可以得到[PtNi(CO)]（ = 2-6）。这些新的合金纳米簇合物的分子结构已通过单晶 X 射线衍射确定。通过计算研究了它们金属笼内 Pt 和 Ni 的位置偏好。还研究了[PtNi(CO)]（ = 3.11）的电化学和 IR 光谱电化学行为，并与同结构的均相纳米簇[Pt(CO)]进行了比较。
