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Title

New iridathiaboranes with reversible isonido ↔ nido cluster Flexibility

AuthorsBould, Jonathan; Cunchillos, Carmen ; Lahoz, Fernando J. ; Oro, Luis A. ; Kennedy, J. D.; Macías, Ramón
Issue Date2010
PublisherAmerican Chemical Society
CitationInorganic Chemistry 49(16): 7353-7361 (2010)
AbstractThe reaction between [IrCl(CO)(PMe3)2] and the Cs[arachno-6-SB9H12] salt in CH2Cl2 yields pale-yellow 11-vertex [8,8,8-(CO)(PMe3)2-nido-8,7- IrSB9H10] (4). Reaction of this CO-ligated iridathiaborane with Me3N -O affords pale-yellow 11-vertex [1,1,1-(H)(PMe 3)2-isonido-1,2-IrSB9H9] (6), which is also formed from the thermal decarbonylation of 4. Compound 4 has a conventional cluster structure based on classical 11-vertex nido geometry, with the iridium center and the sulfur atom in the adjacent 8-and 7-positions on the pentagonal open face. Compound 6 exhibits an 11-vertex isonido structure based on an octadodecahedron with the {Ir(H)(PMe3)2} occupying the apical position of connectivity six, but with one long non-bonding Ir-B distance generating the quadrilateral isonido open-face. Compound 6 reverts to 4 upon reaction with CO, and the Lewis acid character of 6 is further demonstrated in the reaction with EtNC to give [8,8,8-(EtNC)(PMe 3)2-nido-8,7-IrSB9H10] (7). The three new compounds 4, 6, and 7 have been characterized by single-crystal X-ray diffraction analyses and by NMR spectroscopy. Each of the nido iridathiaboranes 4 and 7 exhibits two different {Ir(L)(PMe3)2}-to-{SB 9H10} conformers in solution and in the solid state. Density functional theory (DFT) calculations reveal that the iridium atom inverts the nido-isonido-closo energy profile previously found for the rhodathiaborane congener [8,8-(PPh3)2-nido-8,7-RhSB 9H10] (3), demonstrating how the structure of these 11-vertex clusters can be controlled and fine-tuned by the tailoring of the metal center. © 2010 American Chemical Society.
URIhttp://hdl.handle.net/10261/53336
DOI10.1021/ic1004769
Identifiersdoi: 10.1021/ic1004769
issn: 0020-1669
e-issn: 1520-510X
Appears in Collections:(ICMA) Artículos
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