Metal complexes

Patent metadata

Field	Value
Publication number	US-9593203-B2
Application number	US-201214233571-A
Country	US
Kind code	B2
Filing date	Jul 18, 2012
Priority date	Jul 18, 2011
Publication date	Mar 14, 2017
Grant date	Mar 14, 2017

Abstract

The present invention provides novel metal complexes, methods of making, and methods of using the same.

First claim

What is claimed is:

1. A metallosalenate complex comprising a cationic bicyclic guanidinium group, wherein the cationic bicyclic guanidinium group has no free amines.

2. The metallosalenate complex of claim 1 , wherein the metallosalenate complex is of formula I:

wherein,
R 1a and R 1a′ independently a hydrogen or an optionally substituted radical selected from the group consisting of C 1-12 aliphatic; C 1-12 heteroaliphatic; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic 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;
each R d is independently a -L-CG group, 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- to 14-membered 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; or 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, wherein at least one occurrence of R d is a -L-CG group;
each L is independently a covalent bond or an optionally substituted, saturated or unsaturated, straight or branched, bivalent C 1-12 hydrocarbon chain, wherein one or more methylene units of L are optionally and independently replaced by -Cy-, —CR 2 —, —NR—, —N(R)C(O)—, —C(O)N(R)—, —N(R)SO 2 —, —SO 2 (R)—, —O—, —C(O)—, —OC(O)—, —OC(O)O—, —C(O)O—, —N(R)C(O)O—, —SiR 2 —, —S—, —SO—, or —SO 2 —;
each CG is independently a cationic bicyclic guanidinium group having no free amines;
each Cy is independently an optionally substituted bivalent ring selected from phenylene, a 3-7 membered saturated or partially unsaturated carbocyclylene, a 3-7 membered saturated or partially unsaturated monocyclic heterocyclylene having 1-2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 5-6 membered heteroarylene having 1-3 heteroatoms independently selected from nitrogen, oxygen;
R 4b is selected from the group consisting of:

where
R c at each occurrence is independently 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- to 14-membered 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; or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; where two or more R c groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more optionally substituted rings;
R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl; C 1-20 aliphatic; C 1-20 heteroaliphatic; carbamoyl; arylalkyl; phenyl; a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7- to 14-membered 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; or 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;
T is a divalent linker selected from the group consisting of: —NR—, —N(R)C(O)—, —C(O)NR—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO 2 —, —SiR 2 —, —C(═S)—, —C(═NR)—, or —N═N—; a polyether; a C 3 to C 8 substituted or unsubstituted carbocycle; and a C 1 to C 8 substituted or unsubstituted heterocycle;
M is a metal atom;
each X is independently a suitable counterion;
k is from 0 to 2, inclusive;
m is from 0 to 6, inclusive;
m′ is from 0 to 4, inclusive;
q is from 0 to 4, inclusive; and
x is from 0 to 2, inclusive.

3. The metallosalenate complex of claim 2 , wherein the metallosalenate complex is of formula II or II-a:

4. The metallosalenate complex of claim 3 , wherein the metallosalenate complex is of formula II-aa, II-bb, II-cc, II-dd, II-ee, II-ff, II-gg, or II-hh:

5. The metallosalenate complex of claim 1 , wherein R 1a and R 1a′ are hydrogen.

6. The metallosalenate complex of claim 2 , wherein M is selected from the group consisting of Cr, Mn, V, Fe, Co, Mo, W, Ru, Al, and Ni.

7. The metallosalenate complex of claim 6 , wherein one occurrence of R d is a -L-CG group, and any other R d groups are an optionally substituted C 1-20 aliphatic group or an optionally substituted phenyl group.

8. The metallosalenate complex of claim 2 , wherein -L- is an optionally substituted, saturated or unsaturated, straight or branched, bivalent C 1-6 hydrocarbon chain, wherein one, two, or three methylene units of L are optionally and independently replaced by -Cy-, —CR 2 —, —NR—, —N(R)C(O)—, —C(O)N(R)—, —N(R)SO 2 —, —SO 2 N(R)—, —O—, —C(O)—, —OC(O)—, —OC(O)O—, —C(O)O—, —N(R)C(O)O—, —SiR 2 —, —S—, —SO—, or —SO 2 —.

9. The metallosalenate complex of claim 8 , wherein -L- is an optionally substituted, saturated or unsaturated, straight or branched, bivalent C 1-6 hydrocarbon chain, wherein one or two methylene units of L are optionally and independently replaced by —NR—, —O—, or —C(O)—.

Assignees

• Allen Scott D
• Farmer Jay J
• Job Gabriel E
• Cherian Anna E
• Novomer Inc

Inventors

• Allen Scott D
• Farmer Jay J
• Job Gabriel E
• Cherian Anna E

Classifications

• C07F15/065

  without a metal-carbon linkage · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title