%0 Generic
%A Darensbourg, Donald J.
%A Ganguly, Poulomi
%A Billodeaux, Damon R.
%D 2004
%T Structural Characterization of Several (CO)3(dppp)MnX
Derivatives, dppp = 1,3-Bis(diphenylphosphino)propane
and X = H, OTs, OC2H5, Cl, Br, or N3. An Assessment of
Their Efficacy for Catalyzing the Coupling of Carbon
Dioxide and Epoxides
%U https://acs.figshare.com/articles/dataset/Structural_Characterization_of_Several_CO_sub_3_sub_dppp_MnX_Derivatives_dppp_1_3_Bis_diphenylphosphino_propane_and_X_H_OTs_OC_sub_2_sub_H_sub_5_sub_Cl_Br_or_N_sub_3_sub_An_Assessment_of_Their_Efficacy_for_Catalyzing_the_Coupling_of_Carbon_Dioxide_and_Epo/3313351
%R 10.1021/om049352v.s001
%2 https://ndownloader.figshare.com/files/5152084
%K Br
%K associative interchange process
%K dppp
%K N 3
%K OT
%K Cl
%K complex
%K 24 h reaction
%K CO 2 insertion
%K OC 2 H 5
%X The X-ray structures of a series of (CO)3(dppp)MnX complexes, X = H, OTs, OEt, Cl, Br,
and N3, and dppp = 1,3-bis(diphenylphosphino)propane, prepared by literature methods are
reported. Several of these derivatives have been examined for their ability to serve as
catalysts for the coupling of cyclohexene oxide and carbon dioxide. Although, these
organometallic complexes do catalyze the formation of polycarbonate, their activity is not
competitive with other very effective catalysts for this coupling reaction. Nevertheless,
findings from these studies contribute significantly to our understanding of this important
process. The complex containing the alkoxide ligand is the most active, yet it possesses a
TON (mol epoxide consumed/mol Mn) of only 50 for a 24 h reaction. In this instance the
(CO)3(dppp)MnOEt complex exists as the carbonate species, (CO)3(dppp)MnOC(O)OEt,
because of rapid CO2 insertion into the Mn−OEt bond. The order of epoxide ring-opening
by the X group (initiator) was found to be −OC(O)OR > Cl ≥ N3 > Br. Furthermore, since
these complexes are substitutionally inert, this process is best defined as occurring via an
associative interchange process and is rate-limiting.
%I ACS Publications