Chemistry of C-Trimethylsilyl-Substituted Heterocarboranes. 14. Syntheses of closo-Indacarboranes and Their Reactivity toward a Bis(bidentate) Lewis Base, 2,2'-Bipyrimidine: Crystal Structures of closo-1-(Me2CH)-1-In-2,3-(SiMe3)2-2,3-C2B4H4 and 1-(2,2'-C8H6N4)-1-(Me2CH)-1-In-2,3-(SiMe3)2-2,3-C2B4H4

Dihydrogen intermolecular contacts in group 13 compounds: H⋯H or E⋯H (E = B, Al, Ga) interactions?

“…A larger number of structures (35) were found with Ga⋯H-Ga contacts at distances around the sum of the van der Waals radii (3.52 Å). In our CSD survey, only one structure was found with a short In-H⋯H-In contact (CSD refcode SITNAK10), 56 which corresponds also to the only short In⋯H contact, 2.96 Å, to be compared with a van der Waals sum of 3.63 Å. Finally, no Tl-H⋯H-Tl short intermolecular contacts were found in our CSD survey.…”

Recent Advances in the Chemistry of Heterocarborane Complexes Incorporating s- and p-Block Elements

“…The structure of the gallacarborane is shown in Figure ; the structure of the indacarborane is quite similar ,− Figure gives the structure of the bipyrimidine−gallacarborane complex, 1-(2,2‘-C 8 H 6 N 4 )-1-( t -C 4 H 9 )-2,3-(SiMe 3 ) 2 -1,2,3-GaC 2 B 4 H 4 , the structure of the corresponding bipyridine complex was also determined and found to be quite similar to the one shown in Figure . Therefore, this structure is probably typical of the base−gallacarborane adducts.…”

“…Much of the structural work on the half-sandwich gallacarboranes, and their base complexes, have been duplicated in the indacarboranes. , Except that it crystallizes as a dimer, the structure of the uncomplexed “carbons adjacent” indacarborane, 1-[Me 2 CH]- 2,3-(SiMe 3 ) 2 -1,2,3-InC 2 B 4 H 4 is very similar to the structure shown in Figure , in that the metal occupies the apical position above the C 2 B 3 bonding face and is slightly slip distorted toward the unique boron (see Table ); this slip distortion is also greatly enhanced by coordination of the indium with a base, giving adduct geometries similar to that shown in Figure . The same arguments used in rationalizing the geometries of the gallacarboranes can be applied to the corresponding indacarboranes.…”

“…The same arguments used in rationalizing the geometries of the gallacarboranes can be applied to the corresponding indacarboranes. The observed differences can be attributed to the fact that the metal−carborane interactions are more ionic in the indacarboranes than those found in the corresponding gallacarboranes …”

Evolution of C2B4Carborane Chemistry: from Early Years to the Present

“…These same distortions were also present in the trimethylsilyl-substituted gallacarborane closo -1-( t -C 4 H 9 )-2,3-(SiMe 3 ) 2 -1,2,3-GaC 2 B 4 H 4 and the indacarborane closo -1-(Me 2 CH)-2,3-(SiMe 3 ) 2 -1,2,3-InC 2 B 4 H 4 . The group 13 metals were found to act as Lewis acid sites and formed complexes with a number of Lewis bases, such as bipyridine (2,2‘-C 10 H 8 N 2 ) and bipyrimidine (2,2‘-C 8 H 6 N 4 ). ,− Structural studies show that, on coordination with the base, the slip distortion of the metal increases and the base is oriented over the boron side of the C 2 B 3 bonding face. The increased slip distortion observed on base complexation in the gallacarboranes has been explained using the molecular orbital calculations .…”