Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent

A catalyst of formula (III):

• wherein
• a) M is independently Mg(II), Ca(II), Ge(II) or Ge(IV)-(X)2,
• R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an amine, an imine, an ether group, a silyl ether group or an acetylide group or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alicyclic or heteroalicyclic group;
• R3 is independently optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
• R4 is independently H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
• R5 is H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
• E1 is C and E2 is O, S or NH;
• or E1 is N and E2 is O;
• G is absent or independently a neutral or anionic donor ligand which is a Lewis base;
• wherein when both instances of G are absent and all instances of R5 are hydrogen, X is independently OC(O)RZ, OSO(RZ)2, OSO2RY, OSORT, ORV, phosphinate, hydroxyl, carbonate, nitrate or optionally substituted aryl, heteroaryl, alicyclic or heteroalicyclic, RZ is independently hydrogen or optionally substituted C2-20aliphatic, C2-20haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl;
• RY is hydrogen or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl with the proviso that RY is not C7H7;
• RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroaliyclic;
• RT is hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl;
• and wherein when either one or both instances of G are not absent, or one or more instances of R5 is not hydrogen, X is independently OC(O)Rx, OSO2Rx, OSORx, OSO(Rx)2, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
• Rx is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl;
• R1, R2, R3, R4, R5, Rx, RV, RY, RZ and RT are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
• or
• b) M is independently Zn(II), Co(II), Mn(II), Ti(II), Fe(II), Cr(II), Cr(III)-X, Co(III)-X, Mn(III)-X, Fe(III)-X, Al(III)-X, Ti(III)-X, V(III)-X or Ti(IV)-(X)2,
• G is absent or independently a neutral or anionic donor ligand which is a Lewis base;
• R5 is H, or optionally substituted aliphatic, alicyclic, aryl, or alkylaryl;
• E1 is C and E2 is O, S or NH;
• or E1 is N and E2 is O;
• wherein
• i) when both instances of G are absent and all instances of R5 are hydrogen, X is independently OC(O)RZ, OSO(RZ)2, OSO2RY, OSORT, ORV, phosphinate, hydroxyl, carbonate, nitrate or optionally substituted aryl, heteroaryl, alicyclic or heteroalicyclic;
• R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide group or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl or alicyclic group;
• R3 is independently optionally substituted alkylene, alkenylene, alkynylene, arylene or cycloalkylene, wherein alkylene, alkenylene or alkynylene may optionally be interrupted by aryl or alicyclic;
• R4 is independently H, or optionally substituted aliphatic, alicyclic, aryl, or alkylaryl;
• RZ is independently hydrogen or optionally substituted C2-20aliphatic, C2-20haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl;
• RY is hydrogen or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl or alkylaryl with the proviso that RY is not C7H7;
• RV is optionally substituted aryl, haloaryl, heteroaryl, heteroaliphatic, alicyclic, alkylaryl or heteroaliyclic;
• RT is hydrogen, or optionally substituted aliphatic, haloaliphatic, alicyclic, aryl or alkylaryl;
• R1, R2, R3 and R4 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic or unsubstituted aryl;
• and
• RV, RY, RZ and RT are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
• ii) when either one or both instances of G are not absent, X is independently OC(O)Rx, OSO2Rx, OSORx, OSO(Rx)2, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
• Rx is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl;
• R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an amine, an ether group, a silyl ether group, or an acetylide group or an optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl, heteroaryl, alicyclic or heteroalicyclic;
• R3 is optionally substituted alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, arylene, heteroarylene or cycloalkylene, wherein alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene and heteroalkynylene may optionally be interrupted by aryl, heteroaryl, alicyclic or heteroalicyclic;
• R4 is H, or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, heteroaryl, alkylheteroaryl or alkylaryl;
• and
• R1, R2, R3, R4, R5 and Rx are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
• or
• iii) when or one or more instances of R5 are not hydrogen, X is independently OC(O)Rx, OSO2Rx, OSORx, OSO(Rx)2, ORx, phosphinate, halide, nitrate, hydroxyl, carbonate, amido or optionally substituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
• Rx is independently hydrogen, or optionally substituted aliphatic, haloaliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl, alkylaryl or heteroaryl;
• R1 and R2 are independently hydrogen, halide, a nitro group, a nitrile group, an imine, an ether group, a silyl ether group or an acetylide group or optionally substituted alkyl, alkenyl, alkynyl, haloalkyl, aryl or alicyclic group;
• R3 is independently optionally substituted alkylene, alkenylene, alkynylene, arylene or cycloalkylene, wherein alkylene, alkenylene or alkynylene may optionally be interrupted by aryl or alicyclic;
• R4 is independently H, or optionally substituted aliphatic, alicyclic, aryl, or alkylaryl;
• R1, R2, R3, R4 and R5 are each independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, imine, nitrile, acetylide, unsubstituted aliphatic, unsubstituted alicyclic or unsubstituted aryl;
• and
• Rx is independently optionally substituted by halogen, hydroxyl, nitro, carbonate, alkoxy, aryloxy, heteroaryloxy, amino, alkylamino, imine, nitrile, acetylide, or unsubstituted aliphatic, heteroaliphatic, alicyclic, heteroalicyclic, aryl or heteroaryl;
• with the proviso that the catalyst is not:
• [Co2LCl2(CH3OH)2].H2O,
• [Co2LBr2(CH3OH)2].H2O,
• [Mn2LCl2(CH3OH)2].H2O,
• [Mn2LBr2(CH3OH)2].H2O,
• [CoIICoIIILCl2Br(CH3OH)].0.5CH2Cl2,
• [MnIIMnIIILCl2Br(CH3OH)], or
• [FeIICoIIL(μ-OAc)(OAc)(H2O)],
• wherein L is