0000000000280392
AUTHOR
Norma Siguero
Part 2. Synthesis, characterization and X-ray structure of a new enantiomerically pure bis-equatorial dirhodium(II) compound
Abstract The UV irradiation of an acetone solution of Rh2(O2CCF3)4 and the chiral phosphane (1S, 2S, 5R)-(2-hydroxy-5-isopropenyl-2-methyl-cyclohexyl)diphenylphosphane, (+)PPh2(CHR*OH) leads to the formation of two diastereoisomeric bis-equatorial compounds of formula Rh2(μ-O2CCF3)2(η1-O2CCF3)2(η2-(+)PPh2(CHR*OH))2 P(+)2 and M(+)2 in a 1.5:1 ratio, respectively. Both compounds have been separated by standard column chromatography. The characterization of the enantiomer M(+)2 has been accomplished by X-ray crystallography. The molecular structure consists of an Rh2 4+ unit bridged by two trifluoroacetate ligands. The coordination of each metal center is fulfilled by one phosphine acting …
Reaction of Tris(2-thienyl)phosphine with Dirhodium(II) Acetate. Orthometalation of a Heteroaromatic π-System and an Unusual Ring Rearrangement
The reaction of tris (2-thienyl)phosphine (1) with dirhodium(II) acetate in a 9:1 refluxing toluene/ acetic acid mixture for 2 h leads to the formation of two metalated compounds. The structure of one of them contained two new orthometalated phosphines in a head-to-head arrangement, and, surprisingly, the metalated thiophene rings, but not the nonmetalated ones, were rearranged to a 3-thienyl structure. Both types of dirhodium compounds were assessed in a catalytic α-diazo ester transformation.