SYNTHESIS, STRUCTURE, AND REACTIVITY OF CHIRAL RHENIUM CYCLOALKENE COMPLEXES OF THE FORMULA [(ETA-5-C5H5)RE(NO)(PPH3)(CH = CH(CH2)N-2)]+BF4- - FACILE VINYLIC DEPROTONATION OF A COORDINATED ALKENE Academic Article uri icon

abstract

  • Reactions of [(5C5H5)Re(NO)(PPh3)(ClC6H5)]+BF4 and (n = 5, a; 6, b; 7, c; 8, d) give cycloalkene complexes (6a d, 94 to 79%). A crystal structure of the methylcyclopentadienyl analog of 6a shows the Re plane and Re PPh3 bond to be coplanar, with the vinyl protons syn to the cyclopentadienyl ligand. Reaction of 6a and tBuOK+ leads to the vinyl complex (9a, 90%) instead of expected allyl complex (10a) Analogous reactions of 6b d give varying mixtures of 9b d/10b d. HBF4 OEt2 and 9a react to form the cyclopentylidene complex (10+ BF4, 96%), the stability of which precludes any intermediacy in the deprotonation of 6a. A crystal structure of 11+ PF6 shows the ReCC planes to be perpendicular to the Re P bond. Spectroscopic features of compounds 6 are analyzed in detail, and NMR data show a high barrier to cyclopentylidene ligand rotation in 11+ BF4 (G (110C) 19 kcal/mol). Copyright 1991 WILEYVCH Verlag GmbH & Co. KGaA, Weinheim

published proceedings

  • CHEMISCHE BERICHTE

author list (cited authors)

  • KOWALCZYK, J. J., ARIF, A. M., & GLADYSZ, J. A.

citation count

  • 33

complete list of authors

  • KOWALCZYK, JJ||ARIF, AM||GLADYSZ, JA

publication date

  • April 1991

publisher