Chemistry of 11-vertex rhodathiaboranes: reactions with monodentate phosphines |
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Authors: | Calvo Beatriz Kess Martin Macías Ramón Cunchillos Carmen Lahoz Fernando J Kennedy John D Oro Luis A |
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Institution: | Instituto Universitario de Catálisis Homogénea, Universidad de Zaragoza, Zaragoza, Spain. |
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Abstract: | The reaction of 8,8-(PPh(3))(2)-nido-8,7-RhSB(9)H(10)] (1) with PR(3) in a 1:2 ratio affords mixtures that contain the mono-substituted bis-PR(3)-ligated rhodathiaboranes 8,8-(PPh(3))(L)-nido-8,7-RhSB(9)H(10)] L = PMe(2)Ph (5), PMe(3) (6)] and the corresponding tris-PR(3)-ligated compounds 8,8,8-(L)(3)-nido-8,7-RhSB(9)H(10)] L = PMe(2)Ph (7), PMe(3) (8)]. These latter species are more conveniently prepared from the reaction of 1 with three equivalents of the monodentate phosphines, PMe(2)Ph and PMe(3). Reaction between 1 and PMePh(2) in a 1:2 ratio yields the disubstituted rhodathiaborane 8,8-(PMePh(2))(2)-nido-8,7-RhSB(9)H(10)] (4), whereas the use of three equivalents of phosphine leads to the formation of B-ligated eleven-vertex 8,8,8-(PMePh(2))(2)(H)-nido-8,7-RhSB(9)H(9)-9-(PMePh(2))] (9). Compounds 4-9 have been characterized by NMR spectroscopy, and the structures of 8 and 9 confirmed by X-ray diffraction analyses. The characterization of the cluster compounds has been aided by the use of DFT calculations on some of the species. Variable-temperature NMR studies have demonstrated a lability of the PMePh(2) ligands in compounds 4 and 9, providing mechanistic insights about the ligand substitutional chemistry in these eleven-vertex rhodathiaboranes. |
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