Nanosized Au4Pd32(CO)28(PMe3)14 Containing a Highly Distorted Encapsulated Au4 Tetrahedron: Proposed Multi-Twinned Growth-Pattern from Two Deformed Au-Centered Double Icosahedral-Based Fragments*

As part of an extensive effort to synthesize a variety of nanosized gold–palladium carbonyl phosphine clusters, the neutral Au₄Pd₃₂(CO)₂₈(PMe₃)₁₄ (1) was isolated and unambiguously characterized by low-temperature CCD X-ray diffraction and IR measurements. This nanosized Au₄Pd₃₂ cluster was prepared in low yields (<5%) from the room-temperature reaction of Pd₁₀(CO)₁₂(PMe₃)₆ (2) with Au(SMe₂)Cl in THF/acetone. The heretofore unknown molecular geometry of 1 of pseudo-D₂ (222) symmetry (without methyl substituents) may be viewed to arise from a relatively strong (Au–Au)-bonded linkage (2.64 Å (av)) of two pentagonal-bipyramidal (μ₅-Au)(μ₅-Pd)Pd₅ polyhedra; this generated 14-atom Au₂Pd₁₂ unit may be considered as a markedly deformed part of a 19-atom Au-centered double icosahedron without the inner pentagon (corresponding to five missing inner atoms). In turn, two Au₂Pd₁₂ units form a central composite-twinned Au₄Pd₂₂ kernel via vertex-fusion of two common Pd atoms along with additional formation of four Pd–Pd bonding, four Au–Pd bonding, and two weaker secondary Au–Au bonding interactions at 2.90 Å (av) (versus the other two diagonal Au–Au nonbonding ones at 3.51 Å (av)); this resulting Au₄Pd₂₂P₈ kernel is augmented by the addition of two triangular Pd₃P core-fragments and four exopolyhedral PdP groups to give the Au₄Pd₃₂P₁₄ framework of 1. This cluster is stabilized by 28 bridging COs, of which 20 are doubly bridging and 8 triply bridging. The largest metal-core diameter of 1 along one pseudo C₂ axis is 1.1 nm. This new type of multi-twinned metal cluster has direct relevance to both ligated and non-ligated (naked) non-crystalline metal nanoparticles, many of which possess multiple twinning and/or disorder.^*Dedicated to Professor F. A. Cotton on the occasion of his 75th birthday in recognition of numerous seminal contributions to modern Inorganic Chemistry. Professor Cotton has a truly unparalleled scientific career in Inorganic Chemistry in terms of the overall composite effects of his highly prolific research productivity, his tremendous impact on former graduate students, postdoctoral associates, and collaborators, and his matchless textbooks/monographs.