Synthesis and Stereochemical/Electrochemical Analyses of Cuboctahedral-Based Pd23(CO) x (PR3)10 Clusters (x=20 with R3=Bu n 3, Me2Ph; x=20, 21, 22 with R3=Et3): Geometrically Analogous Pd23(PEt3)10 Fragments with Variable Carbonyl Ligations and Resulting Implications

This research was an outgrowth of previous reactions with Pd₁₃Ni₁₃(CO)₃₄]^4? which produced a tetragonal crystal form of Pd₂₃(CO)₂₀(PEt₃)₁₀ (1) that has the same cuboctahedral-based Pd₂₃ framework with an identical number of PEt₃ ligands but two fewer CO ligands than the monoclinic crystal form of Pd₂₃(CO)₂₂(PEt₃)₁₀ (3) originally reported from reactions with Pd₁₀(CO)₁₂(PEt₃)₆. A subsequent investigation presented herein to establish whether the carbonyl capacity is influenced by the nature of the phosphine ligands has led to syntheses of Pd₂₃(CO) _x (PR₃)₁₀ R₃=Et₃ (1), Bu ⁿ ₃ (4), and Me₂Ph (5)] with 20 CO ligands (x=20) from corresponding Pd₁₀(CO)₁₂(PR₃)₆ precursors either by deligation with Pd(OAc)₂, CF₃CO₂H, Ni(1,5-COD)₂, NMe₄]₂Ni₆(CO)₁₂], or HCO₂H or by spontaneous enlargement; yields varied from 15 to 79%. Although attempts to obtain the original Pd₂₃(CO)₂₂(PEt₃)₁₀ (3) were unsuccessful, a highly significant outcome was the isolation (one time) of another monoclinic crystal form possessing the triethylphosphine Pd₂₃(CO) _x (PEt₃)₁₀ cluster with 21 COs (2). Both the compositions and atomic arrangements for each of five Pd₂₃ clusters 1a (solvated); 1b (unsolvated); 2, 4, and 5] were unambiguously established from low-temperature single-crystal CCD X-ray crystallographic determinations in accordance with their nearly identical IR carbonyl frequencies. Solution ³¹P{¹H} NMR spectra of 1 and 4 at room temperature displayed three distinct signals with expected integral ratios of 2/4/4 that are consistent with the solid-state structures of Pd₂₃(CO)₂₀(PR₃)₁₀ R₃=Et₃ (1), Bu ⁿ ₃ (4)] remaining intact in solution. The metal-core geometries of all of these Pd₂₃(CO) _x (PR₃)₁₀ clusters, including the thermodynamically stable ones with 20 CO ligands and the kinetic products with additional CO ligands (x=21, 22), are essentially the same. The common Pd₂₃ core may be best described as possessing a centered hexacapped cuboctahedral Pd₁₉ kernel (alternatively denoted as a centered ν₂ Pd₁₉ octahedron) with four edge-connected exopolyhedral wingtip Pd(exo) atoms that reduce the pseudo metal-core symmetry from O_h to D_2h. The 10 PR₃ ligands are linked to the six tetracapped Pd(cap) and four edge-capped wingtip Pd(exo) atoms; the latter four Pd(exo) atoms are each composed of four trigonal-planar Pd(μ₂-CO)₂(PR₃) units. These crystallographic results provide compelling geometrical evidence for a heretofore unknown stereochemical example involving variable carbonyl ligation (x=20, 21, 22) of a close-packed nanosized Pd _n (CO) _x (PR₃) _y cluster (in this case with identical PEt₃ ligands) without significant changes being induced in either the overall metal-core architecture or steric dispositions of the same number of PR₃ ligands. These experimental findings have particular relevance to the long-standing Muetterties cluster/surface science analogy in showing that the different number (as well as different modes) of carbonyl ligations observed in these large metal carbonyl clusters are directly related to pressure-induced dissociative/nondissociative migratory coverages in CO chemisorptions on metal surfaces. The observed expanded capacity of CO coordination on the same Pd₂₃ polyhedron without notable changes in geometry is no doubt a consequence of its virtually nanosized metal-core architecture; distances between outermost centrosymmetrically related pairs of Pd(cap) and Pd(exo) atoms in the Pd₂₃ framework are 0.8 and 0.9 nm, respectively. An electrochemical (CV) study revealed that 1 undergoes one quasi-reversible two-electron reduction to 1 ^2? (E_1/2=?0.91 V) and two consecutive quasi-reversible one-electron oxidations to 1/1 ⁺ at E_1/2=0.08 V and 1 ⁺/1 ²⁺ at E_1/2=0.32 V (THF; Ag/AgCl as reference electrode). A stereochemical/electronic analysis with the isostructural Au₂Pd₂₁(CO)₂₀(PEt₃)₁₀ analogue (9) and resulting implications are given.