Catalytic carbonylation catalysts and methods

A catalyst comprising:

• i) a metal complex of formula (III-a), (III-b), (III-c), (IV-a), (IV-b), (IV-c), (V-a), (V-b), (VI-a), (VI-b), or (VI-c):
• wherein:
• Rc, Rd and Re at each occurrence is independently:
• (Z+)b, wherein:
• is a bond or a linker;
• Z+ is a cationic functional group;
• and
• b is an integer from 1 to 4 inclusive;
• or
• hydrogen, halogen, —OR4, —NRy2, —SRy, —CN, —NO2, —SO2Ry, —SORy, —SO2NRy2;
• —CNO, —NRySO2Ry, —NCO, —N3;
• or an optionally substituted group selected from the group consisting of C1-20 aliphatic;
• C1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• 6- to 10-membered aryl;
• 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
• and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur,
• wherein two or more Rc groups, or two or more Rd groups may be taken together to form one or more optionally substituted rings,
• wherein each Ry is independently hydrogen, or an optionally substituted group selected the group consisting of acyl;
• carbamoyl;
• arylalkyl;
• 6- to 10-membered aryl;
• C1-12 aliphatic;
• C1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• an oxygen protecting group;
• and a nitrogen protecting group;
• or wherein two Ry on the same nitrogen atom are taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur;
• R4 is a hydroxyl protecting group or Ry;
• R12 is selected from the group consisting of:
• a (Z+)b group;
• or an optionally substituted radical selected from the group consisting of C1-20 aliphatic;
• C1-20 heteroaliphatic;
• and phenyl;
• and
• M1 and M2 comprise metal atoms, and may be the same or different;
• and
• ii) at least one anionic metal carbonyl species associated with at least one of Z+.