SYNTHESIS, STRUCTURE, AND REACTIVITY OF CHIRAL RHENIUM CARBOXYLIC AND CARBONIC-ACID ESTER COMPLEXES OF THE FORMULA [(ETA-5-C5H5)RE(NO)(PPH3)(ETA-1-O=C(X)X')]+X''- Academic Article uri icon

abstract

  • Reactions of chlorocarbon complexes [(5-C5H5)Re(NO)(PPh3)(ClX)]+BF4- (X = CH2Cl, C6H5) with (a) methyl formate, (b) methyl acetate, (c) ethyl acetate, (d) phenyl acetate, (e) propiolactone, (f) -butyrolactone, (g) 2H-pyran-2-one, (h) 4H-pyran-4-one, (i) dimethyl carbonate, (j) ethylene carbonate, and (k) imidazolidone give the corresponding complexes [(5-C6H5)Re(NO)(PPh3)(1-O=C(X)X)]+BF4- (1a-k+BF4-; 87-42% after workup). Reactions of (5-C5H5)Re(NO)(PPh3)(H), Ph3C+PF6-, and esters b,f give 1b,f+PF6- (83-88%). Crystal structures of 1b,f+PF6- show similar ON-Re-O=C torsion angles (27.6 (9), 12.1 (6)) and C=O bond lengths (1.23 (1), 1.236 (7) ), but the ester oxygen is E to the rhenium in the former and Z in the latter. Spectroscopic, structural, and dynamic properties of 1a-k+X- are analyzed in detail. The ester ligands in 1c,f,i+BF4- are readily displaced by acetone and propionaldehyde at room temperature (Lewis basicity order: propionaldehyde > acetone > c,f,i). Analogous substitutions occur with alcohols. 1992, American Chemical Society. All rights reserved.

published proceedings

  • ORGANOMETALLICS

author list (cited authors)

  • SAURALLAMAS, I., DALTON, D. M., ARIF, A. M., & GLADYSZ, J. A.

citation count

  • 17

complete list of authors

  • SAURALLAMAS, I||DALTON, DM||ARIF, AM||GLADYSZ, JA

publication date

  • February 1992