X-Ray crystal structures of five-coordinate (salen)MnN3 derivatives and their binding abilities towards epoxides: chemistry relevant to the epoxide-CO2 copolymerization process.

The synthesis of several (salen)MnN3 complexes in good yields and purities were achieved by the reaction of manganese(III) acetate and H2salen, followed by metathesis of the remaining acetate ligand with an aqueous solution of NaN3. The X-ray structures of two derivatives, where salen=N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediamine and N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexenediamine respectively, were determined. The complexes were shown to be monomeric 5-coordinate derivatives displaying a distorted square pyramidal geometry, and to be d4 high-spin derivatives by solution magnetic moment measurements using the Evans method.

Studies of the carbon dioxide and epoxide coupling reaction in the presence of fluorinated manganese(III) acacen complexes: kinetics of epoxide ring-opening.

Five-coordinate manganese(III) complexes of N, N'-bis(trifluoroacetylacetone)-1,2-ethylenediimine (tfacacen) have been synthesized and structurally characterized by X-ray crystallography. The presence of the electron-withdrawing -CF3 substituents enhances the electrophilicity of the metal center in these (tfacacen)MnX (X=Cl, N3, NCO, NCS) derivatives when compared with their (acacen)MnX (acacen=N, N'-bis(acetylacetone)-1,2-ethylenediimine) analogs. This is demonstrated by the increased propensity of the Mn(III) center in the tfacacen complexes to bind a sixth ligand.

Manganese(III) Schiff base complexes: chemistry relevant to the copolymerization of epoxides and carbon dioxide.

Schiff base complexes of the form (acacen)Mn(III)X (acacen = N,N'-bis(acetylacetone)-1,2-ethylenediimine), where X = OAc, Cl, or N(3), have been evaluated for their ability to couple CO(2) and cyclohexene oxide in the presence of a variety of cocatalysts to provide cyclic or polycarbonates. These complexes proved to be ineffective at catalyzing this process; however, valuable information related to the coordination chemistry of these manganese Schiff bases was elucidated. Of importance, mechanistic findings as revealed by comprehensive studies involving structurally related (salen)CrX and (salen)CoX complexes strongly support the requirement of six-coordinate metal species for the effective copolymerization of CO(2) and epoxides.