Dihydrogen bond
Encyclopedia
In chemistry
, a dihydrogen bond is a kind of hydrogen bond
, an interaction between a metal hydride bond and an OH or NH group or another proton
donor. The first example of this phenomenon is credited to Brown and Heseltine. They observed intense absorptions in the IR bands at 3300 and 3210 cm−1 for a solution of (CH3)2NHBH3. The higher energy band is assigned to a normal N−H vibration whereas the lower energy band is assigned to the same bond, which is interacting with the B−H. Upon dilution of the solution, the 3300 cm−1 band increased in intensity and the 3210 cm−1 band decreased, indicative of intermolecular association.
Interest in dihydrogen bonding was reignited upon the crystallographic characterization of the molecule H3NBH3
. In this molecule, like the one studied by Brown and Hazeltine, the hydrogen atoms on nitrogen have a partial positive charge, denoted Hδ+, and the hydrogen atoms on boron have a partial negative charge, often denoted Hδ−. In other words, the amine is a protic acid and the borane end is hydridic. The resulting B−H...H−N attractions stabilize the molecule as a solid. In contrast, the related substance ethane
, H3CCH3, is a gas with a boiling point 285 °C lower. Because two hydrogen atoms are involved, this is termed a dihydrogen bond.
Formation of a dihydrogen bond is assumed to precede formation of H2 from the reaction of a hydride and a protic acid. A very short dihydrogen bond is observed in NaBH4·2H2O with H−H contacts of 1.79, 1.86, and 1.94 Å.
This kind of H−H interaction is distinct from the H−H bonding interaction in transition metal
complexes having dihydrogen bound to a metal. Another so-called hydrogen hydrogen bond is postulated to exist in certain compounds between two neutral non-bonding hydrogen atoms.
Chemistry
Chemistry is the science of matter, especially its chemical reactions, but also its composition, structure and properties. Chemistry is concerned with atoms and their interactions with other atoms, and particularly with the properties of chemical bonds....
, a dihydrogen bond is a kind of hydrogen bond
Hydrogen bond
A hydrogen bond is the attractive interaction of a hydrogen atom with an electronegative atom, such as nitrogen, oxygen or fluorine, that comes from another molecule or chemical group. The hydrogen must be covalently bonded to another electronegative atom to create the bond...
, an interaction between a metal hydride bond and an OH or NH group or another proton
Proton
The proton is a subatomic particle with the symbol or and a positive electric charge of 1 elementary charge. One or more protons are present in the nucleus of each atom, along with neutrons. The number of protons in each atom is its atomic number....
donor. The first example of this phenomenon is credited to Brown and Heseltine. They observed intense absorptions in the IR bands at 3300 and 3210 cm−1 for a solution of (CH3)2NHBH3. The higher energy band is assigned to a normal N−H vibration whereas the lower energy band is assigned to the same bond, which is interacting with the B−H. Upon dilution of the solution, the 3300 cm−1 band increased in intensity and the 3210 cm−1 band decreased, indicative of intermolecular association.
Interest in dihydrogen bonding was reignited upon the crystallographic characterization of the molecule H3NBH3
Ammonia borane
Ammonia borane is the chemical compound with the formula H3NBH3. The colourless solid is the simplest molecular boron-nitrogen-hydride compound and has attracted attention as a source of hydrogen fuel.-Synthesis:...
. In this molecule, like the one studied by Brown and Hazeltine, the hydrogen atoms on nitrogen have a partial positive charge, denoted Hδ+, and the hydrogen atoms on boron have a partial negative charge, often denoted Hδ−. In other words, the amine is a protic acid and the borane end is hydridic. The resulting B−H...H−N attractions stabilize the molecule as a solid. In contrast, the related substance ethane
Ethane
Ethane is a chemical compound with chemical formula C2H6. It is the only two-carbon alkane that is an aliphatic hydrocarbon. At standard temperature and pressure, ethane is a colorless, odorless gas....
, H3CCH3, is a gas with a boiling point 285 °C lower. Because two hydrogen atoms are involved, this is termed a dihydrogen bond.
Formation of a dihydrogen bond is assumed to precede formation of H2 from the reaction of a hydride and a protic acid. A very short dihydrogen bond is observed in NaBH4·2H2O with H−H contacts of 1.79, 1.86, and 1.94 Å.
This kind of H−H interaction is distinct from the H−H bonding interaction in transition metal
Transition metal
The term transition metal has two possible meanings:*The IUPAC definition states that a transition metal is "an element whose atom has an incomplete d sub-shell, or which can give rise to cations with an incomplete d sub-shell." Group 12 elements are not transition metals in this definition.*Some...
complexes having dihydrogen bound to a metal. Another so-called hydrogen hydrogen bond is postulated to exist in certain compounds between two neutral non-bonding hydrogen atoms.