Reactivity electrocatalytic substitution

In the mid-1960s, Dessy and coworkers [12, 13] provided an extensive survey of the anodic and cathodic reactions of transition metal organometallic species, including binary (homoleptic) carbonyls, and this provided a stimulus for many later detailed studies. Whereas the electrochemistry of heteroleptic transition metal carbonyls is covered elsewhere in this volume, that of the binary carbonyls, which is covered here, provides paradigms for the electrochemistry of their substituted counterparts. A key aspect is the generation of reactive 17-electron or 19-electron intermediates that can play key roles in the electrocatalytic processes and electron-transfer catalysis of CO substitution by other ligands. 

Among ordered bimetallic systems, the Pt-Sn one can be considered at present as the most in-depth studied not only for its surface structural properties, but also for its reactivity and catalytic properties. A comparable detailed knowledge exists only for a few other cases, among platinum alloys we can cite the Ni-Pt and Co-Pt systems, examined for their catalytic properties and the Pt-Ti system studied for their electrocatalytic properties [5]. Sparse data relative to the surface properties of several other Pt alloys exist (e.g. FeaPt and CuaPt -[3] and PtaMn [51]. All these data available pertain to fee phases either random substitutional or ordered compounds. Data exist also for other cubic ordered alloys which are isostructural with the PtaSn compound, e.g. NiaAl [52, 53] and AuaPd [28] and finally the Au-Cu system, which has been object of interest as the prototypical LI2 or Pm3m ordered system in the CuaAu composition [54, 55]. 

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