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

The 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.

(1-Ferrocenyl-4,4,4-trifluorobutane-1,3-dionato-κ2O,O)bis(triphenylphosphane)copper(I)

“…The coordination geometry around copper(I) is best described as a distorted tetrahedron that resembles other complexes including (hfac)Cu(1,5-COD), see: Pampaloni et al (2005); Doyle et al (1985), or (Me 3 P) 2 Cu(acac), see: Shin et al (1991); Chi et al (1992). The bond distances Cu-P, Cu-O, Fe-D1 (1.6401 (9) Å) and Fe-D2 (1.6466 (9) Å) (D1 = centroid of C1 -C5; D2 = centroid of C6 -C10) as well as the bond angles P2-Cu1-P1, P2-Cu1-O1, P2-Cu1-O2, P1-Cu1-O1, P1-Cu1-O2, O2-Cu1-O1 are similar to those ones found for other copper(I) β-diketonate derivatives, see, for example: Yang et al (2001); Marchetti et al (2000); Croxtall et al (2003); Herberhold et al (2004). The atoms Cu1, O1, O2, and C11 -C13 are, as expected, in plane bound (r. m. s. d. of a calculated mean plane = 0.024 Å).…”

“…For applications of Cu(I)-hexafluoroacetonates, see: Pampaloni et al (2005); Doyle et al (1985). For other copper(I) -diketonate derivatives, see: Yang et al (2001); Marchetti et al (2000); Croxtall et al (2003); Herberhold et al (2004). For a related ferrocenyl derivative of the title compound, see: du Plessis et al (1999).…”