pubs.acs.org/Organometallics Published on Web 02/10/2010 r 2010 American Chemical Society Organometallics 2010, 29, 1231–1237 1231 DOI: 10.1021/om100024c Increasing the Curvature of a Bowl-Shaped Polyarene by Fullerene-like η 2 -Complexation of a Transition Metal at the Interior of the Convex Surface Alexander S. Filatov, † Andrey Yu. Rogachev, ‡ Edward A. Jackson, § Lawrence T. Scott, § and Marina A. Petrukhina* ,† † Department of Chemistry, University at Albany, State University of New York, Albany, New York 12222, ‡ Institute f € ur Anorganische und Angewandte Chemie, Universit € at Hamburg, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany, and § Merkert Chemistry Center, Department of Chemistry, Boston College, Chestnut Hill, Massachusetts, 02467-3860 Received January 7, 2010 The first transition metal complex of monoindenocorannulene, [{Rh 2 (O 2 CCF 3 ) 4 } 2 3 (C 26 H 12 )] (1), has been synthesized by gas-phase deposition and has been structurally characterized by X-ray crystal- lography. In the solid state, it forms a 2D organometallic network based on intermolecular Rh-C interactions and rare tetra-bridged coordination of a π-bowl. In addition to η 2 -rim binding, one Rh(II) center interacts exclusively with interior carbon atoms on the convex surface, exhibiting an η 2 -coordination type previously observed only in closed, all-carbon buckyballs. The latter unique coordination of Rh(II) accentuates the pyramidalization of the C atoms of monoindenocorannulene. Thus, in contrast to all other reported Rh(II) complexes with buckybowls, metal complexation leads to a curvature increase of the C 26 H 12 core in 1. DFT calculations (PBE0) reveal the preferred coordination sites of C 26 H 12 to be the rim of the corannulene core, followed by the interior spoke and then the rim CC bonds of the indeno site. This calculated trend is nicely followed by the average Rh-C bond distances in the solid-state structure of 1: 2.567 (rim) < 2.687 (spoke) < 2.715 A ˚ (indeno site). The nature of Rh(II)-π interactions was quantitatively evaluated in terms of ligand-to-metal and metal-to-ligand contributions, showing the consistently greater role of the former in all computed complexes. 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