How innocent is thallium(I)? Corrected formulations of [Tl2Pd14(CO)9(PMe3)11][PF6]2 and [TlPd9(CO)9(PPh3)6][PF6] clusters previously reported as corresponding Au2Pd14 and AuPd9 clusters

Evgueni G. Mednikov; Lawrence F. Dahl

doi:10.1039/C2CC37959G

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Chemical Communications

Issue 11, 2013

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How innocent is thallium(I)? Corrected formulations of [Tl₂Pd₁₄(CO)₉(PMe₃)₁₁][PF₆]₂ and [TlPd₉(CO)₉(PPh₃)₆][PF₆] clusters previously reported as corresponding Au₂Pd₁₄ and AuPd₉ clusters

Evgueni G. Mednikov*^a and Lawrence F. Dahl*^a

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Department of Chemistry, University of Wisconsin-Madison, Madison, USA
E-mail: mednikov@chem.wisc.edu

Chem. Commun., 2013,49, 1085-1087

DOI: 10.1039/C2CC37959G
Received 02 Nov 2012, Accepted 12 Dec 2012
First published online 14 Dec 2012

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Abstract
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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 Image ID:c2cc37959g-t2.gif 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.