Dihydrogen complex

Dihydrogen complexes are coordination complexes containing intact H2 as a ligand. They are a subset of sigma complexes. The prototypical complex is W(CO)3(PCy3)2(H2). This class of compounds represent intermediates in metal-catalyzed reactions involving hydrogen. Hundreds of dihydrogen complexes have been reported. Most examples are cationic transition metals complexes with octahedral geometry.

Upon complexation, the HH bond is extended to 0.81–0.82 Å as indicated by neutron diffraction, about a 10% extension relative to the HH bond in free H2. Some complexes containing multiple hydrogen ligands, i.e. polyhydrides, also exhibit short HH contacts. It has been suggested that distances < 1.00 Å indicates significant dihydrogen character, where separations > 1 Å are better described as dihydride complexes (see figure).

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