Planar Tetracoordinate Hydrogen: Pushing the Limit of Multicentre Bonding.

Among the list of planar tetracoordinate atoms, the smallest element hydrogen is missing. No experimental and theoretical evidence have ever been put forwarded. Herein, we introduce the first planar tetracoordinate hydrogen atom (ptH) in the global minimum geometry of In H cluster. Bonding analysis indicates that the central hydrogen atom is acting like a proton and significant charge transfer from the surrounding In framework results in a negative charge of the central hydrogen atom. The proposed global minimum geometry possesses σ-aromaticity and the central hydrogen atom forms unusual multicentre bond with more than three centres.