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Ligand additions to Cp{sup *}(CO){sub 2}Re=Re(CO){sub 2}Cp{sup *} and fragmentation and rearrangement reactions of Cp{sup *}(CO){sub 2}Re({mu}-CO)Re(CO)(L)Cp{sup *}

Journal Article · · Organometallics
DOI:https://doi.org/10.1021/om9509507· OSTI ID:263201
; ; ;  [1]
  1. Univ of Wisconsin, Madison, WI (United States)
Cp{sup *}(CO){sub 2}Re=Re(CO){sub 2}Cp{sup *} (1) is a rare example of a dimer of a d{sup 6} 16 electron metal fragment. Here we report that the addition of 2-electron donor ligands to 1 produces a series of tetracarbonyl complexes Cp{sup *}(CO){sub 2}Re({mu}-CO)Re(CO)(L)Cp{sup *} [L=CO (2), PMe{sub 3} (5), CH{sub 3}CN (6), CH{sub 2}=CH{sub 2} (7), CH{sub 3}C=V@CCH{sub 3} (8)] which have interesting stereochemistries and display fascinating fluxional behavior. The observation of a 2-butyne complex is particularly important since such alkyne complexes are likely intermediates in the formation of both dimetallacyclopentenones and dimetallacyclobutenes. The conversion of the 2-butyne adduct 8 to the dimetallacyclopentenone Cp{sup *}(CO){sub 2}Re[{mu}-{eta}{sup 1},{eta}{sup 3}-(CH{sub 3})-C=C(CH{sub 3})CO]Re(CO)Cp{sup *} (9) and the fluxional behavior of 9 that requires a symmetric dimetallacyclobutene or dimetallabicyclobutane intermediate is also presented. 36 refs., 3 figs., 2 tabs.
OSTI ID:
263201
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 11 Vol. 15; ISSN ORGND7; ISSN 0276-7333
Country of Publication:
United States
Language:
English