Nanosized Pd37(CO)28{P(p-Tolyl)3}12 containing geometrically unprecedented central 23-atom interpenetrating tri-icosahedral palladium kernel of double icosahedral units: its postulated metal-core evolution and resulting stereochemical implications.

Pd37(CO)28{P(p-Tolyl)3}12 (1) was obtained in approximately 50% yield by the short-time thermolysis of Pd10(CO)12{P(p-Tolyl)3}6 in THF solution followed by crystallization via layering with hexane under N2. The low-temperature (100 K) CCD X-ray diffraction study of 1 revealed an unusual non-spheroidal Pd37-atom polyhedron, which may be readily envisioned to originate via the initial formation of a heretofore non-isolated central Pd23 kernel composed of three interpenetrating trigonal-planar double icosahedra (DI) that are oriented along the three bonding edges of its interior Pd3 triangle. This central Pd23 kernel is augmented by face condensations with two additional phosphorus-free and 12 tri(p-C6H4Me)phosphine-ligated Pd atoms, which lower the pseudo-symmetry of the resulting 37-atom metal core from D(3h) to C2. The 12 P atoms and 28 bridging CO connectivities preserve the pseudo-C2 symmetry. The central Pd23 kernel in 1 provides the only crystallographic example of the 23-atom member of the double icosahedral family of "twinned" interpenetrating icosahedra (II), which includes the 19-atom two II (1 DI), the 23-atom three II (3 DI), the 26-atom four II (6 DI), and the 29-atom five II (9 DI). The n-atoms of these DI models coincide exactly with prominent atom-peak maxima of 19, 23, 26, and 29, respectively, in the mass spectrum of charged argon clusters formed in a low-temperature free-jet expansion. The only previous crystallographically proven 26- and 29-atom DI members are the central pseudo-T(d) tetrahedral Pd26 kernel (4 II, 6 DI) in the PMe3-ligated Pd29Ni3(CO)22(PMe3)13 (2) and the central pseudo-D(3h) trigonal-bipyramidal Pd29 kernel (5 II, 9 DI) in the PMe3-ligated Pd35(CO)23(PMe3)15 (3). Two highly important major stereochemical implications are noted: (1) The formation of geometrically identical idealized architectures for these three II palladium kernels with corresponding DI models constructed for the charged argon clusters provides compelling evidence that the nature of delocalized Pd-Pd bonding in these II (and presumably other nanosized) Pd clusters, in which each zerovalent Pd atom individually has a closed-subshell 4d (10) ground state, may likewise (as in argon clusters) be viewed primarily in terms of (considerably stronger) attractive dispersion interactions. (2) The existence of the 23-atom II Pd23 kernel in 1 provides an essential heretofore "missing" geometrical link as an intermediate in the same sequential growth pathway to give the 26- and 29-atom II Pd(n) kernels found in 2 and 3, respectively. Accommodation of the 12 bulky P(p-Tolyl)3 ligands around the entire 37-atom palladium core necessitates an extended metal surface that originates from the pseudo-2D trigonal-planar Pd23 kernel found in 1. The much smaller PMe3 ligands in 2 and 3 would sterically allow further sequential transformations of an initially formed 23-atom II intermediate palladium kernel into the 26-atom spheroidal II palladium kernel in 2 or further into the 29-atom semi-spheroidal II palladium kernel in 3, but with smaller total metal-atom nuclearities of 32 and 35, respectively.