SYNTHESIS, STRUCTURE, AND REACTIVITY OF (PENTAMETHYLCYCLOPENTADIENYL)RHENIUM ALDEHYDE COMPLEXES [(ETA-5-C5ME5)RE(NO)(PPH3)(ETA-2-O=CHR)]+BF4- - HIGHLY DIASTEREOSELECTIVE DEUTERIDE ADDITIONS Academic Article uri icon

abstract

  • Reactions of the dichloromethane complex [(5-C5Me5)Re(NO)(PPh3)(ClCH2Cl)]+BF4- and RCH=O (R; a, CH3; b, CH2CH3; c, CH(CH3)2; d, C6H5; e, CH2C6H5) give -aldehyde complexes (RS,SR)-[(5- C5Me5Re(NO)(PPh3)(2-O=CHR)]+BF4- ((RS,SR)-5a-e, 85-89%). A crystal structure of [RS,SR)-5b shows the RCH=O carbon to be anti to the PPh3 ligand and the ethyl group to be syn to the NO ligand, confirming the stereochemical assignment. The C-O bond length (1.325 (7) ) is intermediate between that of a single and double bond. Reactions of (RS,SR)-5a-e and formyl complex (5-C5H5)Re(NO)(PPh3)(CHO) (6) give alkoxide complexes (5-C5Me5)Re(NO)(PPh3)(OCH2R) (7a-e, 79-88%) and [(5-C5H5)Re(NO)(PPh3)- (CO)]+BF4- (94%). Analogous reactions with deuterioformyl complex 6-d1 give 7a-e-d1 as 78-98:22-2 mixtures of RR,SS and RS,SR diastereomers. The mechanism of diastereoselection is analyzed. Complexes 7a-e-d1 epimerize at rhenium at room temperature. 1992, American Chemical Society. All rights reserved.

published proceedings

  • ORGANOMETALLICS

author list (cited authors)

  • AGBOSSOU, F., RAMSDEN, J. A., HUANG, Y. H., ARIF, A. M., & GLADYSZ, J. A.

citation count

  • 19

complete list of authors

  • AGBOSSOU, F||RAMSDEN, JA||HUANG, YH||ARIF, AM||GLADYSZ, JA

publication date

  • February 1992