Chromium(II) Acetate - Structure

Structure

The Cr2(OAc)4(H2O)2 molecule contains two atoms of chromium, two ligated molecules of water, and four monoanionic acetate ligands. The coordination environment around each chromium atom consists of four oxygen atoms (one from each acetate ligand) in a square, one water molecule (in an axial position), and the other chromium atom (opposite the water molecule), giving each chromium centre an octahedral geometry. The chromium atoms are joined together by a quadruple bond, and the molecule has D4h symmetry (ignoring the position of the hydrogen atoms). The same basic structure is adopted by Rh2(OAc)4(H2O)2 and Cu2(OAc)4(H2O)2, although these species do not have such short M---M contacts.

The quadruple bond between the two chromium atoms arises from the overlap of four d-orbitals on each metal with the same orbitals on the other metal: the z2 orbitals overlap to give a sigma bonding component, the xz and yz orbitals overlap to give two pi bonding components, and the xy orbitals give a delta bond. This quadruple bond is also confirmed by the low magnetic moment and short intermolecular distance between the two atoms of 236.2±0.1 picometers.The Cr-Cr distances are even shorter, 184 pm being the record, when the axial ligand is absent or the carboxylate is replaced with isoelectronic nitrogenous ligands.

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