A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

Amine-bis(phenolate) chromium(III) chloride complexes 1·THF, 2·THF and 1·DMAP catalyze the copolymerization of cyclohexene oxide and carbon dioxide. These catalysts incorporate tetradentate amine-bis (phenolate) ligands [L1] and [L2], (where [L1] = 2-pyridyl-N,N-bis(2-methylene-4-methoxy-6-tert-butylphenolato) and [L2] = dimethylaminoethylamino-N,N-bis(2-methylene-4-methoxy-6-tert-butylphenolato)) and when combined with 4-(N,N-dimethylamino)pyridine (DMAP) or bis(triphenylphosphoranylidene)ammonium chloride or azide, (PPNCl or PPNN3), yield low molecular weight polycarbonate with narrow dispersities. The structure of 1·DMAP incorporates one molecule of 4-(N,Ndimethylamino)pyridine (DMAP) and can be used as a single-component catalyst precursor. Polymer end group analysis by MALDI-TOF mass spectrometry reveals possible initiation pathways. Scheme 3. (A) Proposed initiation pathway for the copolymerization of cyclohexene oxide and carbon dioxide with 1·DMAP and (B) with 1·DMAP/PPNCl

Magnesium compounds of tetradentate amino-bis(phenolato) ligands, Mg[L1] (1) and Mg[L2] (2) (where [L1] = 2-pyridyl-N,N-bis(2-methylene-4-methoxy-6-tert-butylphenolato), and [L2] = dimethylaminoethylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenolato)) were prepared. The proligands, H2[L1] and H2[L2] were reacted with di(n-butyl)magnesium in toluene to give the desired compounds in high yields. Compounds 1 and 2 exhibit dimeric structures in solutions of non-coordinating solvents as observed by NMR spectroscopy and in the solid state as shown by the single crystal X-ray structure of 2. These compounds exhibit good activity for rac-lactide polymerization in solution and in molten lactide.

Amine-bis(phenolato)chromium(III) chloride complexes, [LCrCl], are capable of catalyzing the copolymerization of cyclohexene oxide with carbon dioxide to give poly(cyclohexane) carbonate. When combined with 4-(N,N-dimethylamino)pyridine (DMAP) these catalyst systems yield low molecular weight polymers with moderately narrow polydispersities. The coordination chemistry of DMAP with five amine-bis(phenolato)chromium(III) chloride complexes was studied by matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The amine-bis(phenolato) ligands were varied in the nature of their neutral pendant donor-group and include oxygen-containing tetrahydrofurfuryl and methoxyethyl moieties, or nitrogen-containing N,N-dimethylaminoethyl or 2-pyridyl moieties. The relative abundance of mono and bis(DMAP) adducts, as well as DMAP-free ions is compared under various DMAP : Cr complex ratios. The [LCr](+) cations show the ability to bind two DMAP molecules to form six-coordinate complex ions in all cases, except when the pendant group is N,N-dimethylaminoethyl (compound ). Even in the presence of a 4 : 1 ratio of DMAP to Cr, no ions corresponding to [L3Cr(DMAP)2](+) were observed for the complex containing the tertiary sp(3)-hybridized amino donor in the pendant arm. The difference in DMAP-binding ability of these compounds results in differences in catalytic activity for alternating copolymerization of CO2 and cyclohexene oxide. Kinetic investigations by infrared spectroscopy of compounds 2 and 3 show that polycarbonate formation by 3 is twice as fast as that of compound 2 and that no initiation time is observed.

Li, Na, K and Ca complexes capable of rac-lactide polymerization in both the melt and in solution were synthesized. MALDI-TOF MS showed mainly cyclic PLA was obtained even in the presence of an alcohol co-initiator.

Chromium(III) chlorido amine-bis(phenolate) complexes paired with nucleophilic co-catalysts are a promising family of catalysts for the copolymerization of CO and epoxides to selectively produce polycarbonates with a very high degree of carbonate linkages. Single-component catalyst systems can be prepared, where the neutral nucleophile, 4-dimethylaminopyridine (DMAP), is coordinated to the metal site to provide a stable octahedral Cr complex. These complexes possess the potential for both anionic (from the chlorido ligand) or neutral (DMAP) nucleophilic epoxide ring-opening during the proposed rate-determining initiation step. Concentration effect studies support a first-order dependence of the polymerization rate on the concentration of single-component catalyst. End-group analysis of polycarbonates by MALDI-TOF MS indicate the presence of predominantly DMAP-initiated chains as well as the occurrence of chain-transfer events resulting in ether linkages, likely from the presence of cyclohexene diol formed by the reaction of cyclohexene oxide and adventitious water.