Self-Assembly of Mercaptane−Metallacarborane Complexes by an Unconventional Cooperative Effect:  A C−H···S−H···H−B Hydrogen/Dihydrogen Bond Interaction

Abstract

The existence of a dihydrogen bond (S-H...H-B) and its combination with a C-H...S hydrogen bond in an unusual cooperative effect are demonstrated from a combination of experimental and theoretical methods. This cooperative effect seems to be responsible for self-assembly of mercaptane-metallacarborane complexes such as closo-[3-Ru(eta6-C6H6)-8-HS-1,2-C2B9H10] (1) and closo-[3-Co(eta5-C5H5)-8-HS-1,2-C2B9H10] (3), which present identical supramolecular two-dimensional polymeric networks. The findings, besides documenting structurally the first S-H...(H-B)2 dihydrogen bond and the unconventional cooperative ability of a boron-attached SH group, prove that substituted carboranes have the potential to serve as building blocks for assembling complex structures.

Interaction of Carboranes with Biomolecules: Formation of Dihydrogen Bonds

“…[15,16] The former method is the standard in deriving partial atomic charges for simulations with the AMBER force field, while the latter is commonly used in quantum chemical calculations and has also been utilized for carboranes. [8,17] Since the partner molecules (amino acids, peptides, DNA bases) have a very non-uniform distribution of accessible proton donors and proton acceptors, the evaluation of the complex structure is a rather difficult problem. Standard gradient optimization techniques, which yield only the nearest local minimum, are not sufficient for finding the global minimum.…”

The Role of C–H···H–B Interactions in Establishing Rotamer Configurations in Metallabis(dicarbollide) Systems

“…[14] To the best of our knowledge the C-H···H-B and other dihydrogen bonds (DHBs) have never been used before to interpret the higher stability of one rotamer vs. another in the solid state, although they have been studied in metallacarborane, [15] carborane [16] or borane derivatives. [10,17] This is one of the targets of this work.…”

Cooperativity between the Dihydrogen Bond and the N⋅⋅⋅HC Hydrogen Bond in LiH–(HCN)nComplexes

“…There are a few studies on its cooperativity with other types of hydrogen bonds. [32] Herein, we systematically study the cooperativity of the dihydrogen bond with the N···HC hydrogen bond in LiH-HCN-HCN and LiH-HCN-HCN-HCN complexes by employing quantum chemi-…”