The Wade–Mingos rules in seven-vertex dimetallaborane chemistry: Hydrogen-rich Cp2M2B5H9 systems of the second and third row transition metals

Polyhedral [M2B5] Metallaborane Clusters and Derivatives: An Overview of Their Structural Features and Chemical Bonding

“…Different structures were predicted for each metal, depending upon their electronic requirement, which in most cases, could be related to the Wade-Mingos electron counting rules. Gratifyingly, the bicapped trigonal bipyramid structure of 2' and 3' (Cp analogs of 2 and 3) were found largely thermodynamically more stable than all other possible geometries, consistent with the experimental observation [68].…”

“…Later, King and coworkers studied various possible geometries for [(CpM) 2 B 5 H 9 ] clusters with early and late transition metals of the second and third rows including the experimentally known species 2 and 3 [68]. Different structures were predicted for each metal, depending upon their electronic requirement, which in most cases, could be related to the Wade-Mingos electron counting rules.…”

“…The examples of this kind of M 2 B 5 species mostly range among the early transition metals such as group 5 in [(CpV) 2 B 5 H 11 ] [ 58 ] and [(Cp*Ta) 2 B 5 H 11 ] [ 59 ], group 6 in [(Cp*M) 2 B 5 H 9 ] (M = Cr, Mo, W) [ 60 , 61 , 62 , 63 , 64 , 65 ], and group 7 in [(Cp*Re) 2 B 5 Cl 5 H 2 ] [ 24 ] (Cp = C 5 H 5 , Cp* = C 5 Me 5 ). Due to their unique structure, thorough theoretical studies were performed by us and others in order to get some insight into their electronic structure and chemical bonding [ 66 , 67 , 68 , 69 , 70 ]. Later, many heterometallic [ 63 , 71 , 72 , 73 , 74 ] and chalcogenated derivatives of oblatonido-M 2 B 5 [ 75 , 76 , 77 , 78 ] were reported in the literature, which are isostructural as well as isoelectronic.…”

Dimetallaborane analogues of the octaboranes of the type Cp2M2B6H10: structural variations with changes in the skeletal electron count

“…Ir 29 ). This paper reports a comprehensive study of the eightvertex systems Cp 2 M 2 B 6 H 10 and Cp* 2 M 2 B 6 H 10 (M = Pd, Pt, Rh, Ir, Ru, Os, Re, Mo, W, Ta) using density functional theory methods similar to those used in the previous studies [12][13][14] on the 5-, 6-, and 7-vertex systems. We studied not only systems with unsubstituted cyclopentadienyl ligands (Cp) but also those with pentamethylcyclopentadienyl ligands (Cp*) as found in the experimentally known Cp* 2 M 2 B 6 H 10 structures (M = Rh, 9 W 21 ).…”