Pd₅₉(CO)₃₂(PMe₃)₂₁:  A Nanosized Metal Cluster Containing a Trigonal D₃ Pd₅₉ Core with 11 Interior Palladium Atoms

Syntheses, structures and properties of primarily nanosized homo/heterometallic palladium CO/PR 3 -ligated clusters

“…Complementary pathways involve generation of reactive 'naked' (highly coordinatively unsaturated) [Pd] species in situ (equations (2.7) and (2.8)) that, (Tran et al 1998(Tran et al , 2001 (Wittayakun 2000).…”

Condensation of Nickel–Carbonyl Clusters with Soft Lewis Acids: Synthesis and Characterisation of the {Cd2Cl3[Ni6(CO)12]2}3– Dimer

“…[1,26] The formation of acid-base adducts, i.e. [Ni 6 (CO) 6 (µ 3 -CO) 5 4-, [24] was previously observed only in the case of InX 3 . This can be explained by the fact that both Cd II and In III are electropositive elements quite difficult to reduce, which form very weak homometallic bonds and with a high affinity for halides Electrochemistry suggests that the two [Ni 6 (CO) 12 ] subunits present in the dimer are electronically independent.…”

“…1.5 nm. More-or-less spherical or ellipsoidal clusters, such as [Ni 32 Pt 24 (CO) 56 ] 6-, [3] [Ni 26 Pd 20 (CO) 54 ] 6-, [4] Pd 59 (CO) 32 -(PMe 3 ) 21 , [5] Pd 69 (CO) 36 (PEt 3 ) 18 [6] and the giant three-shell Pd 145 (CO) x (PEt 3 ) 30 (x ≈ 30), [7] display metallic core diameters in the 1-2-nm range. Moreover, several MCC aggregates close to or trespassing in the nanofield can be prepared, for instance by the fusion of two or more anionic clusters with a central core constituted by a single cation, for example {Hg[Os 10 C(CO) 24 ] 2 } 2-, [8] or cationic moieties, such as [H 2 Ru 12 Cu 6 Cl 2 (CO) 34 ] 2-, [9] [H 4 Ru 20 Cu 6 Cl 2 -(CO) 48 ] 4- [10] and [Ag 3 Ru 10 C 2 (CO) 28 Cl] 2-.…”

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

“…Palladium is a unique transition metal in that it forms an exceptionally versatile family of high‐nuclearity palladium carbonyl phosphine clusters (i.e., with cores of at least 10 metal atoms with direct metal–metal bonding) that display a truly remarkable diversity of geometries about the metal cores 1a–h. Fifteen distinctly different geometries have been identified crystallographically for Pd n cores with n =10,2a–c 12,2d,e 16,2f,g 23 (two different metal cores have been observed),2h–j 29,2e 30,2k 34,1a, 2l 35,2g 38,2m 39,2g 54,2k 59,2g,n 69,2o and 145 2p. All but two of these highly condensed palladium clusters have close‐packed frameworks that contain metal fragments whose structural units may be described as ccp (cubic close‐packed), mixed ccp/hcp (hexagonal close‐packed) stacking layers (which include layer sequences corresponding to capped octahedra, centered cuboctahedra, or centered anti‐cuboctahedra), and as icosahedra.…”

“…One exception is the Pd 38 cluster, which has a highly irregular geometry about the metal core;1a, 2m the other exception is one of the Pd 23 clusters, which has a highly distorted body‐centered‐cubic metal framework 2j. Close‐packed structural units of the Pd n cores also include “twinned interpenetrating” centered cuboctahedral and icosahedral geometries as well as one mixed, face‐fused icosahedral/octahedral Pd 59 architecture, which consists of two centered icosahedra that trans ‐cap a bioctahedron 2g,n. The largest known crystallographically determined discrete metal cluster, Pd 145 , contains a capped three‐shell 145‐atom metal core, whose geometry closely conforms to I h icosahedral symmetry 2p…”