Synthesis of Gold(I) fluoroalkyl and fluoroalkenyl-substituted phosphine complexes and factors affecting their crystal packing

A series of gold(I) phosphine complexes of the type [AuCl{PR2(Rf)}] (R = Et, i-Pr, Cy; Rf = CF[double bond, length as m-dash]CF2; R = Ph, Rf = CF[double bond, length as m-dash]CFH, CCl[double bond, length as m-dash]CF2, C[triple bond, length as m-dash]CCF3, CF3, i-C3F7, s-C4F9) have been prepared and most have been structurally characterised. All of the complexes are monomeric in the solid state, and a number of secondary interactions are observed including short intramolecular AuF distances, metal-bound AuClH non-classical hydrogen bonds, fluorous domains and phenyl embraces. Only in the case of [AuCl{PEt2(CF[double bond, length as m-dash]CF2)}] is an aurophilic interaction with an AuAu contact less than the sum of the van der Waals radii observed. Even then, the distance, 3.3458(10) , is longer than that previously observed for the related complex with R = Ph; Rf = CF[double bond, length as m-dash]CF2.