Syntheses and structures of missing links among polybromocyclopentadienyl rhenium and manganese tricarbonyl complexes Academic Article uri icon


  • Reactions of diazocyclopentadiene and NBS at appropriate stoichiometries give 2,5-dibromodiazocyclopentadiene and 2,3,5-tribromodiazocyclopentadiene in 40% and 30% yields, respectively, after chromatography. These react with BrRe(CO) 5 or BrMn(CO) 5 (80C, CF 3C 6H 5) to give ( 5-1,2,3-C 5H 2Br 3)M(CO) 3 (3; M = a, Re; b, Mn) and ( 5-C 5HBr 4)M(CO) 3 (4a,b) in 75-85% yields. In the case of 4a, the intermediate 1- cyclopentadienyl complex ( 1-C 5HBr 4)Re(CO) 5 (4a) can be isolated (44%). An isomer of 3b, ( 5-1,2,4-C 5H 2Br 3)Mn(CO) 3, is accessed by desilylating previously reported ( 5-1,2,4-C 5(SiMe 3) 2Br 3)Mn(CO) 3 with CsF/MeOH (85%). The reaction of tetrabromodiazocyclopentadiene and BrRe(CO) 5 at 80C in CF 3C 6H 5 gives the 1- cyclopentadienyl complex ( 1-C 5Br 5)Re(CO) 5 (5a, 74%) which cannot be induced to decarbonylate to ( 5-C 5Br 5)Re(CO) 3 (5a) under a variety of conditions. However, 5a can be isolated (45%) when a similar reaction is conducted at 120C. The IR properties of the preceding complexes are compared, and the crystal structures of 3a, 3b, 5a, and 5a are determined and analyzed. 2004 Elsevier B.V. All rights reserved.

published proceedings

  • Journal of Organometallic Chemistry

author list (cited authors)

  • Dinh, L. V., Hampel, F., & Gladysz, J. A.

citation count

  • 8

complete list of authors

  • Dinh, Long V||Hampel, Frank||Gladysz, JA

publication date

  • January 2005