Synthesis and Characterization of [Ru@Ge₁₂]^3–: An Endohedral 3-Connected Cluster

Abstract

The 12-vertex endohedral cluster [Ru@Ge12](3-) reveals an unprecedented D2d-symmetric 3-connected polyhedral geometry. The structure contrasts dramatically with the known deltahedral or approximately deltahedral geometries of [M@Pb12](2-) (M = Ni, Pd, Pt) and [Mn@Pb12](3-) and is a result of extensive delocalization of electron density from the transition-metal center onto the cage.

[V@Ge8As4]3−and [Nb@Ge8As6]3−: encapsulation of electron-poor transition metal atoms

“…4 For both the (empty) 12-atom and 14-atom cluster shells, each atom is bonded to three neighbors. 10,11 For a better understanding of the rather new 12-vertex clusters, the calculations on hypothetical [Rh@Ge 12 ] 3À and the diamagnetic analog to [Ru@Ge 12 ] 3À were included.…”

Intermetalloid Clusters: Molecules and Solids in a Dialogue

“…[34a, 69] In af urther step,t he endohedrally filled species can then serve as precursor for the synthesis of ternary intermetalloid clusters,s uch as [Co@Sn 9 Ni(CO)] 3À and [Co@Sn 9 AuPh] 3À . [70] Non-deltahedral endohedrally filled clusters [M@Ge 10 ] 3À (M = Co,F e) [71] or [Ru@Ge 12 ] 3À [72] emerge upon the fragmentation of the nine-atomic precursor clusters.…”

“…[15] These include metal species like thiolateligated Au n (SR) x with fcc kernels (e.g.for n = 28, 36, 44, …), [16] as well as metal clusters of group 13 and 14 elements mimicking cut-outs of their respective element modifications. To name just one example,m ulti-shell core structures based on icosahedral Mackay-type packing motifs,are observed for the polynuclear palladium kernels of [Pd 55 (P i Pr 3 ) 12 (CO) 20 ], [18] or the cluster giants [Pd 145 (CO) x (PEt 3 ) 30 ]( x % 60, Figure 2) and [(m 12 -Pt)Pd (164Àx) Pt x (CO) 72 (PPh 3 ) 20 ](x % 7). To name just one example,m ulti-shell core structures based on icosahedral Mackay-type packing motifs,are observed for the polynuclear palladium kernels of [Pd 55 (P i Pr 3 ) 12 (CO) 20 ], [18] or the cluster giants [Pd 145 (CO) x (PEt 3 ) 30 ]( x % 60, Figure 2) and [(m 12 -Pt)Pd (164Àx) Pt x (CO) 72 (PPh 3 ) 20 ](x % 7).…”

Intermetalloide Cluster: Moleküle und Festkörper im Dialog

“…[68] Die Koordination eines Zintl-Clusters an ein Metallatom kann auch als erster Schritt hin zur Bildung eines endohedral gefüllten Clusters angesehen werden. [70] Nicht-deltaedrische gefüllte Cluster [M@Ge 10 ] 3À (M = Co,F e) [71] oder [Ru@Ge 12 ] 3À [72] entstehen nach Neuanordnung des neunatomigen Precursor-Clusters. [34a,69] In einem weiteren Schritt kann diese endohedral gefüllte Spezies als Precursor fürd ie Synthese von ternären intermetalloiden Clustern dienen, wie zum Beispiel [Co@Sn 9 Ni(CO)] 3À und [Co@Sn 9 AuPh] 3À .…”