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• W2092127932 abstract "Treatment of [RhCl(η4-diene)]2 (diene = nbd, cod) with the N-heterocyclic ligands 2,2‘-bipyridine (bpy), 4,4‘-dimethyl-2,2‘-bipyridine (Me2bpy), 1,10-phenanthroline (phen), and pyridine (py) followed by addition of Cs[arachno-6-SB9H12] affords the corresponding salts, [Rh(η4-diene)(L2)][SB9H12] [diene = cod, L2 = bpy (1), Me2bpy (3), phen (5), (py)2 (7); diene = nbd, L2 = bpy (2), Me2bpy (4), phen (6), (py)2 (8)]. These compounds are characterized by NMR spectroscopy and mass spectrometry, and in addition, the cod−Rh species 1 and 3 are studied by X-ray diffraction analysis. These saltlike reagents are stable in the solid state, but in solution the rhodium(I) cations, [Rh(η4-diene)(L2)]+, react with the polyhedral anion [SB9H12]- leading to a chemistry that is controlled by the d8 transition element chelates. The nbd−Rh(I) complexes react faster than the cod−Rh(I) counterparts, leading, depending on the conditions, to the synthesis of new rhodathiaboranes of general formulas [8,8-(L2)-nido-8,7-RhSB9H10] [L2 = bpy (9), Me2bpy (10), phen (11), (py)2 (12)] and [8,8-(L2)-8-(L‘)-nido-8,7-RhSB9H10] [L‘ = PPh3, L2 = bpy (13), Me2bpy (14), phen (15); L‘ = NCCH3, L2 = bpy (16), Me2bpy (17), phen (18)]. Compound 13 is characterized by X-ray diffraction analysis confirming the 11-vertex nido-structure of the rhodathiaborane analogues 14−18. In dichloromethane, 1 and 3 yield mixtures that contain the 11-vertex rhodathiaboranes 9 and 10 together with new species. In contrast, the cod−Rh(I) reagent 5 affords a single compound, which is proposed to be an organometallic rhodium complex bound exo-polyhedrally to the thiaborane cage. In the presence of H2(g) and stoichiometric amounts of PPh3, the cod−Rh(I) reagents, 1, 3, and 5, afford the salts [Rh(H)2(L2)(PPh3)2][SB9H12] [L2 = bpy (19), Me2bpy (20), phen (21)]. Similarly, in an atmosphere of CO(g) and in the presence of PPh3, compounds 1−6 afford [Rh(L2)(PPh3)2(CO)][SB9H12] (L2 = bpy (22), Me2bpy (23), phen (24)]. The structures of 19 and 24 are studied by X-ray diffraction analysis. The five-coordinate complexes [Rh(L2)(PPh3)2(CO)]+ undergo PPh3 exchange in a process that is characterized as dissociative. The observed differences in the reactivity of the nbd−Rh(I) salts versus the cod−Rh(I) analogues are rationalized on the basis of the higher kinetic lability of the nbd ligand and its faster hydrogenation relative to the cod diene." @default.
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• W2092127932 date "2007-07-11" @default.
• W2092127932 modified "2023-10-18" @default.
• W2092127932 title "Square-Planar Rhodium(I) Complexes Partnered with [<i>arachno</i>-6-SB₉H₁₂]^-: A Route toward the Synthesis of New Rhodathiaboranes and Organometallic/Thiaborane Salts" @default.
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• W2092127932 doi "https://doi.org/10.1021/ic700648z" @default.
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