Acid/base-controlled AuI/Au0 reductive transformations of the monogold [(μ14-Au)Pd22(CO)20(PEt3)8]+ monocation into three different neutral digold nanoclusters: Au2Pd21(CO)20(PEt3)10, Au2Pd28(CO)26(PEt3)10, and new five-layer hexagonal close-packed (μ12-Au)2Pd42(CO)30(PEt3)12 with a trigonal-bipyramidal AuPd3Au kernel.

Abstract

The monogold [(μ(14)-Au)Pd(22)(CO)(20)(PEt(3))(8)](+) nanocation (2, with a [(CF(3)CO(2))(2)H](-) counterion) is shown to be a versatile precursor for the generation of three different neutral Au-Pd nanoclusters with double gold content in their distinctly dissimilar bimetallic architectures. These carbon monoxide (CO)-induced conversions are based on the reduction of Au(I) to Au(0) that is controlled by the reaction medium. Under basic and acidic conditions, the known Au(2)Pd(21)(CO)(20)(PEt(3))(10) (3; >90% yield) and Au(2)Pd(28)(CO)(26)(PEt(3))(10) (4; ∼40% yield), respectively, were obtained, whereas neutral conditions gave rise to the new (μ(12)-Au)(2)Pd(42)(CO)(30)(PEt(3))(12) (1; ∼10-20% yield; all yields based on gold). The molecular structure of 1, established from a 100 K CCD X-ray diffraction study, consists of a five-layer hexoganol close-packed (hcp) Au(2)Pd(42) framework of pseudo-D(3)h symmetry (crystallographic D(3) site symmetry) of the Pd(6)/AuPd(9)/Pd(12)/AuPd(9)/Pd(6) layer sequence, with the Au atoms centering two identical hcp (μ(12)-Au)Pd(12) face-fused anti-cuboctahedral fragments. The 12 Et(3)-attached P atoms are coordinated to the triangular vertex Pd atoms in the four outer layers (except the middle Pd(12)); all five layers are stapled by interlayer bridging COs. The radial Au(cent)-Pd mean distance of 2.79 Å within the two symmetry-equivalent (μ(12)-Au)Pd(12) anti-cuboctahedral fragments of 1 is identical with the radial Pd(cent)-Pd mean distances within hcp (μ(12)-Pd)Pd(12) anti-cuboctahedral fragments of the two geometrically related nondistorted layered structures of Pd(52)(CO)(36)(PEt(3))(14) and [Ni(9)Pd(33)(CO)(41)(PPh(3))(6)](4-) ([PPh(4)](+) counterion), indicating a strain-free structural effect upon the substitution of Au for Pd in their analogous hcp layer-stacked arrangements. It provides prime evidence for an extension to 1 of our previous self-consistent experimental/theoretical-based hypothesis for delocalization of the 6s valence Au electrons in Au(2)Pd(21) (3) and Au(2)Pd(28) (4) toward a formal closed-shell Au(+) configuration that is electronically equivalent to that of zerovalent Pd.