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Two previously reported cationic clusters, Au2Pd14 (1-Me) and AuPd9 (2-Ph), obtained by similar reactions of CO/PR3-ligated Pd(0) clusters with in the presence of TlPF6 are shown to be [Tl2Pd14(CO)9(PMe3)11]2+ (1a-Me) and [TlPd9(CO)9(PPh3)6]+ (2a-Ph), respectively. These clusters ([PF6]− counterion) were prepared without the presence of gold by reactions of either Pd10(CO)12(PMe3)6 or Pd10(CO)12(PPh3)6 with TlPF6 and characterized crystallographically and spectroscopically.
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