Mixed platinum‐gold clusters. Synthesis, structure and properties of PtAu8(PPh3)8(NO3)2

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Abstract
PtAu8(PPh3)8(NO3)2 is formed by the reaction of H2 with Au(PPh3)NO3 and either Pt(PPh3)3 or Pt(COD)(NO3)2. The metal frame is a centred crown, with a phosphine bonded to each peripheral metal atom. 31P NMR and Mössbauer spectroscopy showed that Pt is in the centre and that the 8 Au atoms are on the crown. A FAB mass spectrum confirmed the indicated composition and showed that no hydrides are present. In an electrochemical study, the cluster could be reduced in two reversible one‐electron steps at ‐1.14 and ‐1.29 V vs SSCE. The growth of the PtAun clusters is discussed in terms of oxidative addition of H2 to Pt and electrophilic substitution of AuPPh3+.