Intramolecular non-covalent interactions in nido-carboranes and metallacomplexes thereof

Non-covalent interactions play a pivotal role in the design of a new material with specific properties [1]. Intermolecular interactions in carboranes are known an important role in formation of solid state structures of... [ view full abstract ]

Non-covalent interactions play a pivotal role in the design of a new material with specific properties [1]. Intermolecular interactions in carboranes are known an important role in formation of solid state structures of carboranes and metallacarboranes [2,3], however intramolecular non-covalent bonds in carboranes are much less studied. In this contribution we describe the role of intramolecular hydrogen bonding between the dicarbollide ligands in transition metals bis(dicarbollide) complexes [3,3’-M(1,2-C₂B₉H₁₁)₂]^- in stabilization of their different rotational isomers (rotamers) (Figure 1) as well as formation of new types of intramolecular B-H…π(C≡C) hydride (Figure 2) and X…H-B halogen-hydride (Figure 3) bonds in nido-carborane derivatives based on single-crystal X-ray and NMR spectroscopy studies and quantum-chemical calculations.

Acknowledgment. This work was supported by the Russian Science Foundation (16-13-10331).

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