Synthesis and x-ray structure of 10-vertex palladium carbonylphosphine cluster with minimal PBun3 content

High-nuclearity palladium carbonyl trimethylphosphine clusters containing unprecedented face-condensed icosahedral-based transition-metal core geometries: proposed growth patterns from a centered Pd13 icosahedron†

“…Structural/bonding features of Pd 16 (CO) 13 (PMe 3 ) 9 (a) Pd 16 (CO) 13 (PMe 3 ) 9 1. The configuration of 1 is presented in Fig.…”

“…(d) Pd 59 (CO) 32 (PMe 3 ) 214. Each of the identical two halves of the 59-atom metal core consists of a centered icosahedron which is partially covered by a layer of18 Pd atoms [with the exclusion of Pd(9) and its two threefold-related Pd(9A) and Pd(9B)]. Each half is composed of 31 atoms, of which four form an interior Pd(i) 4 tetrahedron [viz., the icosahedral-centered Pd(5), and Pd(1) together with its two threefoldrelated Pd(1A),Pd(1F)].…”

Palladium carbonyl complexes

“…Analysis of the Raman and IR spectra of carbonyl molecules containing isotope-substituted CO fragments ( 12 C 16 O, 13 C 16 O, 12 C 18 O) showed that the Pd(CO) 4 molecule is tetrahedral like Ni(CO) 4 (T d symmetry). 33 The frequency of the stretching vibration active in these spectra (the T 2 band) is 2066 cm 71 ; the frequency of the A I vibration, active in the Raman spectrum, is 2122 cm 71 and the force constant k CO = 17.48 mdyn # A 71 in the Cotton ± Kraihanzel approximation. It is of interest that the force constant k CO for the more stable Ni(CO) 4 molecule is virtually the same (17.23 mdyn # A 71 ).…”

“…33 The frequency of the stretching vibration active in these spectra (the T 2 band) is 2066 cm 71 ; the frequency of the A I vibration, active in the Raman spectrum, is 2122 cm 71 and the force constant k CO = 17.48 mdyn # A 71 in the Cotton ± Kraihanzel approximation. It is of interest that the force constant k CO for the more stable Ni(CO) 4 molecule is virtually the same (17.23 mdyn # A 71 ). The M ± C stretching vibrational frequency and force constant are more sensitive to the nature of the central atom.…”

Nanosized [Pd52(CO)36(PEt3)14] and [Pd66(CO)45(PEt3)16] Clusters Based on a Hypothetical Pd38 Vertex‐Truncated ν3 Octahedron

“…The exceptions reported to date are the Pd 12 cluster, which was isolated only with P n Bu 3 2d and PPh 3 ,2e and the Pd 35 ,2g Pd 39 ,2g and Pd 59 2g,n clusters, which were obtained only with sterically smaller PMe 3 ligands. Furthermore, all of the triethylphosphine‐containing [Pd n (CO) x L y ] (L=PEt 3 ) clusters may be obtained from reactions with the same tetracapped octahedral Pd 10 precursor, [Pd 10 (CO) 12 (PEt 3 ) 6 ],2b,c through different kinetically controlled synthetic pathways to give relatively thermodynamically stable products in most cases. For the majority of the Pd n clusters, reasonably good yields (at least 30 %) were ultimately obtained by optimization of the reaction conditions and in particular cases by the structure‐to‐synthesis approach from different synthetic routes.…”