Five-Coordinate Hydrogen: Neutron Diffraction Analysis of the Hydrido Cluster Complex [H2Rh13(CO)24]3−

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Science  21 Feb 1997:
Vol. 275, Issue 5303, pp. 1099-1102
DOI: 10.1126/science.275.5303.1099

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Pentacoordinate hydrogen atoms were identified by single-crystal neutron diffraction analysis of [N(CH3)4]3[H2Rh13(CO)24]. The hydrogen atoms are located in square pyramidal cavities of the Rh13 cluster, in positions almost coplanar with the Rh4 faces on the surface of the cluster. They are slightly displaced inward, toward the central rhodium atom of the cluster, with average H-Rh(central) and H-Rh(surface) distances of 1.84(2) and 1.97(2) angstroms, respectively. This result shows that hydrogen, which normally forms only one bond, can be attached to five other atoms simultaneously in a large metal cluster.

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