Stability of the gold(I)-phosphine bond. A comparison with other group 11 elements

Peter Schwerdtfeger, Holger L. Hermann, Hubert Schmidbaur

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The stability of gold phosphine complexes of the form [Au(PH3)n]+ (n = 1-4) and [AuCl(PH3)n] (n = 1-3) is analyzed in detail by applying quantum theoretical methods and compared to the coordination behavior of the lighter group 11 elements copper and silver. It is shown that, once [M(PH3)2]+ or [MClPH3] (M = Cu, Ag, and Au) is formed, further coordination by PH3 ligands is relatively weak; i.e., the energy gain to form [M(PH3)3]+ from [M(PH3)2]+ is less than 60 kJ mol-1, and less than 100 kJ mol-1 to form [MCl(PH3)2] from [MClPH3]. Relativistic effects in gold significantly influence these factors and reduce the tendency for phosphine coordination beyond two-coordination. This implies that the most favored coordination number for gold is two with either a linear P-Au-P or P-Au-X arrangement (X = a strongly coordinating ligand like Cl-). Instead, X-Au-PH3 units prefer to interact via close Au-Au contacts (aurophilic interactions) keeping the linear structure approximately intact, while the corresponding copper and silver compounds prefer PH3 coordination to strongly bound M2Cl2 units (M = Cu or Ag) where two chlorine atoms bridge the two metal atoms thus having the formal coordination number of three for copper or silver.

Original languageEnglish
Pages (from-to)1334-1342
Number of pages9
JournalInorganic Chemistry
Issue number4
StatePublished - 24 Feb 2003
Externally publishedYes


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