Synthesis and chemistry of chiral rhenium acyls (.eta.-C5H5)Re(NO)(PPh3)(COR) Academic Article uri icon

abstract

  • Rhenium acyls (η-C 5 H 6 )Re(NO)(PPH 3 )(COR) (R = CH 3 (2), CH 2 CH 3 (3), CH 2 -n-C 8 H 17 (4), C 6 H 6 (5), CH 2 C 6 H 6 (6), CH 2 CH 2 CeH 5 (7), CH=CH 2 (8), CH 2 CH=CH 2 (9)) are prepared in high yield by RMgX attack upon (η-C 5 H 5 )Re(NO)(PPH 3 )(COOCH 3 ) (1). Acyl (η-C 5 H 5 )Re(NO)(PPH 3 )(COC=CCH 3 ) (10) is prepared by LiC=CCH 3 attack upon [(η-C 5 H 5 )Re(NO)(PPH 3 )(CO)] + BF 4- . Acyls 2, 5, and 7 are also prepared in optically active form from optically active 1. These compounds are characterized by IR, 1 H NMR, 13 C NMR, and (when optically active) ORD and CD. They are shown to undergo high-yield (1) BH 3 reduction ((-)-{R)-2, 4, (+)-(R)-5, 7) to the corresponding alkyls (η-C 5 H 5 )Re(NO)(PPH 3 )(CH 2 R), (2) methylation with CH 3 SO 3 F/NH 4+ PF 6- (2, 5) to methoxycarbenes [(η-C 5 H 5 )Re)NO)(PPH 3 )(=C(OCH 3 )R)] + PF 6- , and (3) protonation with CF 3 SO 3 H (2, 3) to hydroxycarbenes [(η-C 5 H 5 )Re(NO)(PPH 3 )(=C(OH)R) + CF 3 SO 3- . Structures for the preferred conformers of 2-10 and their methylation and protonation products are suggested. © 1983, American Chemical Society. All rights reserved.

author list (cited authors)

  • Buhro, W. E., Wong, A., Merrifield, J. H., Lin, G. Y., Constable, A. C., & Gladysz, J. A.

citation count

  • 37

publication date

  • December 1983