Synthesis of [(Cp*Re)2BnHn]n=8-10: Metal Boride Particles That Stretch the Cluster Structure Paradigms

Designing a non-icosahedral twelve-vertex deltahedral metallatricarbaborane with a degree 7 metal vertex

“…Thus, the preference of the three carbon atoms in B8C3Mo-1 for non-adjacent degree 4 vertices drives the system towards rearrangement to give an unusual 12-vertex deltahedron with a degree 7 vertex. In the set of 12-vertex deltahedra linked by sequences of dsd processes, the B8C3Mo-1 deltahedron can also be considered to be a link between the regular icosahedron with all degree 5 vertices and the experimentally known [6][7][8][9] Cp* 2 Re 2 B 10 H 10 deltahedron with two degree 7 vertices. The next three CpMoC 3 B 8 H 11 structures in terms of relative energies, namely B8C3Mo-2, B8C3Mo-3, and B8C3Mo-4, are based on the same deltahedron as found experimentally [9] in [{[η 3 -C 3 H 5 )(OC) 2 Mo} [(PhC)(CH)B 9 H 9 ] − with the molybdenum atom at one of the degree 6 vertices.…”

“…Transition metals, in particular, can prefer locations at vertices of degrees higher than five. An extreme example is the experimentally known dirhenaborane Cp* 2 Re 2 B 10 H 10 having each rhenium atom at a degree 7 vertex, four boron atoms at degree 4 vertices, and the remaining six boron atoms at degree 5 vertices [5][6][7][8]. In addition, the 12-vertex molybdadicarbaborane monoanion [{[η 3 -C 3 H 5 )(OC) 2 Mo} [(PhC)(CH)B 9 H 9 ] − has been shown by X-ray crystallography to have a non-icosahedral deltahedral structure with two degree 6 vertices, two degree 4 vertices, and eight degree 5 vertices [9].…”

The relevance of boranes and metallaboranes to the structures of p-block element nanoparticles

“…Thus, the reaction of (Cp * Re) 2 B 4 H 8 with borane or chloroborane permitted the isolation of dirhenaboranes containing 5 through 10 boron fragments [24,25]. The homologous closo-series shown in Fig.…”

Geometry and chemical bonding in polyhedral boranes, metallaboranes, and dimetallaboranes: From closo to isocloso to oblatocloso polyhedra

“…These highly oblate deltahedra, found so far only in dimetallaboranes of Group 6 and Group 7 transition metals, are conveniently called oblatocloso deltahedra to differentiate them from the closo and isocloso deltahedra for metal-free boranes and metallaboranes with a single metal atom, respectively. The most complete set of stable known compounds exhibiting oblatocloso deltahedral structures are found in the cyclopentadienylrhenium dimetallaboranes Cp 2 Re 2 B nÀ2 H nÀ2 (8 6 n 6 12; Cp = an g 5 -cyclopentadienyl ligand, most commonly g 5 -Me 5 C 5 ) [14][15][16].…”