84330-26-7Relevant articles and documents
Novel ylide-type rhodium complexes containing a six-membered RhCH2PR2CH2CH2PR2 ring
Werner, Helmut,Hofmann, Lothar,Paul, Wilfried,Schubert, Ulrich
, p. 1106 - 1111 (2008/10/08)
The chelate rhodium(I) complexes C5H3Rh[1,2-C2H4(PR2) 2] (2, R = Ph; 3, R = Me) have been prepared from [L2RhCl]2 (L = C2H4, C8H14), the diphosphine (dppe or dmpe), and MC5H5 (M = Na, Tl). Compounds 2 and 3 react with CH2I2 by oxidative addition to give the (iodomethyl)rhodium(III) compounds [C5H5RhCH2I(1,2-C2H 4(PR2)2)]I (4a, 5a) which have been converted by reaction with NH4PF6 to the more stable PF6 salts 4b and 5b. Whereas 4b is completely inert in nitromethane solution, 5b on addition of NEt3 isomerizes quantitatively to give the metallaheterocycle [C5H5(I)RhCH2PMe2CH 2CH2PMe2]PF6 (7). The corresponding dicationic derivative [C5H5(PMe3)RhCH2PMe 2CH2CH2PMe2](PF6) 2 (8) is obtained by ligand exchange. The molecular structure of 7 has been determined by X-ray analysis. Compound 7 crystallizes in the space group P21/n with a = 848.2 (2) pm, b = 1489.5 (4) pm, c = 1594.6 (4) pm, and β = 103.17 (2)°. The six-membered ring in the cation of 7 adopts a chair conformation. Complex 7 has also been prepared from C5H5RhCH2I[P(OMe)3]I and dmpe in the presence of NH4PF6. In contrast, the analogous (iodomethyl)rhodium compound C5H5RhCH2I(PMe3)I reacts with dmpe (and NH4PF6) to produce a dinuclear-bridged species which presumably has the composition {[C5H5(PMe3)(I)Rh]2(μ-CH 2PMe2CH2CH2PMe2CH 2)}(PF6)2 (9). The cobalt complexes C5H5Co(dmpe) (12), [C5H5(CO)Co]2(μ-dmpe) (13), C5H5Co(CO)(η1-dppm) (14), and [C5H5CoCOCH3(η2-dppm)]I (15) also have been prepared by using either C5H5Co(PMe3)2 or C5H5Co(CO)2 as starting material.
