The Structure of the Ligand Tri(1-cyclohepta-2,4,6-trienyl)phosphane, P(C7H7)3, in the Hexafluoroacetylacetonato Copper(I) Complexes, (hfac)Cu[P(C7H7)3]n (n = 1, 2)

Abstract

AbstractThe reaction of CuCl[P(C7H7)3] (1a) with sodium hexafluoroacetylacetonate, Na(hfac), leads to (hfac)Cu[P(C7H7)3] (2a), which in the presence of excess P(C7H7)3 (a) gives (hfac)Cu[P(C7H7)3]2 (3a). Whereas the 1:2 compound 3a is a pseudo-tetrahedral copper(I) complex with relatively long Cu-P (224.85(10) and 223.75(10) pm) and Cu-O (212.7(3) and 212.0(3) pm) distances, the 1:1 complex 2a may be described as having a distorted pseudo-trigonal coordination sphere (Cu-P 214.32(11) pm, Cu-O 196.6(3) and 208.1(3) pm), although one of the cyclohepta-2,4,6-trienyl substituents develops a weak additional interaction with the metal through its central C=C double bond (Cu-C 275.1 and 272.9 pm). The molecular geometries of the tri(1-cyclohepta-2,4,6-trienyl) complexes 2a and 3a are compared with those of the known tri(cyclohexyl)phosphane complexes, (hfac)Cu[P(C6H11)3]n (n = 1 (2b) and 2 (3b)), and related compounds.