| 15332818 |
Vicente J, Gil-Rubio J, Bautista D, Sironi A, Masciocchi N: Synthesis and reactivity of fluoro complexes: Part 2. Inorg Chem. 2004 Sep 6;43(18):5665-75.
Rhodium (I) fluoro complexes with alkene and phosphine ligands. Synthesis of the first isolated rhodium (I) bifluoride complexes. Structure of [Rh3 (mu3-OH) 2 (COD)(3)](HF2) by X-ray powder diffraction.. The reaction between [Rh (mu-OH)(COD)](2) (COD = 1,5-cyclooctadiene) and 73% HF in THF gives [Rh (3)(mu (3)-OH)(2)(COD)(3)](HF (2)) (1). Its crystal structure, determined by ab initio X-ray powder diffraction methods (from conventional laboratory data), contains complex trimetallic cations linked together in 1D chains by a mu (3)-OH...F-H-F...HO-mu (3) sequence of strong hydrogen bonds. The complex [Rh (mu-F)(COE)(2)](2) (COE = cyclooctene; 2), prepared by reacting [Rh (mu-OH)(COE)(2)](2) with NEt (3).3HF (3:2), has been characterized. Complex 1 reacts with PR (3) (1:3) to give [RhF (COD)(PR (3))] [R = Ph (3), C (6) H (4) OMe-4 (4), (i) Pr (5), Cy (6)] that can be prepared directly by reacting [Rh (mu-OH)(COD)](2) with 73% HF and PR (3) (1:2:2). The reactions of 1 with PPh (3) or Et (3) P have been studied by NMR spectroscopy at different molar ratios. Complexes [RhF (PEt (3))(3)] (7), [RhF (COD)(PEt (3))] (8), and [RhF (PPh (3))(3)] (9) have been detected. The complex [Rh (F)(NBD)(iPr (3) P)] (NBD = norbornadiene; 10) was prepared by the sequential treatment of [Rh (mu-OMe)(NBD)](2) with 1 equiv of NEt (3).3HF and (i) Pr (3) P. The first isolated bifluoride rhodium (I) complexes [Rh (FHF)(COD)(PR (3))] [R = Ph (11), (i) Pr (12), Cy (13)], obtained by reacting fluoro complexes 3, 5, and 6 with NEt (3).3HF (3:1), have been characterized. The crystal structures of 3 and 11 have been determined. |
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