Catalysts and methods for polymer synthesis

Patent metadata

Field	Value
Publication number	US-9505878-B2
Application number	US-201514615902-A
Country	US
Kind code	B2
Filing date	Feb 6, 2015
Priority date	Aug 22, 2008
Publication date	Nov 29, 2016
Grant date	Nov 29, 2016

Abstract

The present invention provides unimolecular metal complexes having increased activity in the copolymerization of carbon dioxide and epoxides. Also provided are methods of using such metal complexes in the synthesis of polymers. According to one aspect, the present invention provides metal complexes comprising an activating species with co-catalytic activity tethered to a multidentate ligand that is coordinated to the active metal center of the complex.

First claim

What is claimed:

1. A metal complex having the structure:

wherein:

comprises a tetradentate porphyrin ligand;
M is a metal atom optionally coordinated to up to two nucleophiles capable of ring opening an epoxide; and
(Z) m represents one or more activating moieties tethered to the multidentate ligand, where represents a linker moiety; m represents the number of Z groups present on a linker moiety and is an integer between 1 and 4 inclusive; and each (Z) represents an activating moiety.

2. The metal complex of claim 1 , wherein M is selected from the group consisting of Cr, Co, and Al.

3. The metal complex of claim 1 , wherein M is Cr.

4. The metal complex of claim 1 , wherein M is Co.

5. The metal complex of claim 1 , wherein the metal complex is:

wherein
R d at each occurrence is independently a (Z) m group hydrogen halogen —OR, —NR 2 , —SR, —CN, —NO 2 , —SO 2 R, —SOR, —SO 2 NR 2 ; —CNO, —NRSO 2 R, —NCO, —N 3 , —SiR 3 ; or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; where two or more R d groups may be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms; and
R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C 1-6 aliphatic; C 1-6 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; an oxygen protecting group; and a nitrogen protecting group, where two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring.

6. The metal complex of claim 1 , wherein the moiety contains 1-30 atoms including at least one carbon atom, and optionally one or more atoms selected from the group consisting of N, O, S, Si, B, and P.

7. The metal complex of claim 1 , wherein the moiety is a C 2-30 aliphatic group wherein one or more methylene units are optionally and independently replaced by —NR y —, —N(R y )C(O)—, —C(O)N(R y )—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —Si(R y ) 2 —, —SO—, —SO 2 —, —C(═S)—, —C(═NR y )—, or —N═N—, where each occurrence of R y is independently —H, or an optionally substituted radical selected from the group consisting of C 1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl.

8. The metal complex of claim 1 , wherein the moiety is selected from the group consisting of:

where * represents the site of attachment to the ligand, and each # represents a site of attachment of an activating functional group; and
each occurrence of R y is independently —H, or an optionally substituted radical selected from the group consisting of C 1-6 aliphatic, 3- to 7-membered heterocyclic, phenyl, and 8- to 10-membered aryl.

9. The metal complex of claim 1 , wherein each Z group is independently selected from the group consisting of:

wherein: each occurrence of R′, R 2 and R 3 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein two or more R 1 , R 2 and R 3 groups can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more additional heteroatoms;
R 4′ is hydrogen or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; a 8- to 10-membered aryl; a 5- to 10-membered heteroaryl; 3- to 7-membered heterocyclic; oxide; and hydroxyl;
each occurrence of R 5 and R 6 is independently hydrogen or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle; a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; wherein R 5 and R 6 can be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms, and an R 5 or R 6 group can be taken with an R 1 or R 2 group to form one or more optionally substituted rings;
each occurrence of R 7 is in

Assignees

• Novomer Inc

Inventors

• Allen Scott D
• Cherian Anna E
• Simoneau Chris A
• Farmer Jay J
• Coates Geoffrey W
• Gridnev Alexei
• Lapointe Robert E

Classifications

• B01J31/183

  with more than one complexing nitrogen atom, e.g. phenanthroline · CPC title

• B01J31/182

  comprising aliphatic or saturated rings · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title

• B01J31/16

  containing coordination complexes · CPC title

• C07F15/065 Primary

  without a metal-carbon linkage · CPC title