Catalyst for ring expansion metathesis polymerization of cyclic monomers

• US 10,639,620 B2
• Filed: 09/19/2016
• Issued: 05/05/2020
• Est. Priority Date: 09/18/2015
• Status: Active Grant

• Current Assignee: University of Florida Research Foundation, Incorporated (State University System of Florida)
• Original Assignee: University of Florida Research Foundation, Incorporated (State University System of Florida)
• Inventors: Veige, Adam S., Almeida Gonsales, Stella
• Primary Examiner(s): Qian, Yun
• Application Number:
  US15/760,730
• Publication Number:
  US 20180257065A1
• Time in Patent Office: 1,324 Days
• Field of Search: None
• CPC Class Codes: B01J 2231/14 Other (co) polymerisation, e.g. of lactides, epoxides "ROMP", i.e. ring-opening metathesis polymerisation B01J2231/54
• CPC Class Codes: B01J 2231/543 alkene metathesis
• CPC Class Codes: B01J 2531/0244 Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
• CPC Class Codes: B01J 2531/66 Tungsten
• CPC Class Codes: B01J 2540/10 Non-coordinating groups comprising only oxygen beside carbon or hydrogen
• CPC Class Codes: B01J 2540/225 comprising perfluoroalkyl groups or moieties
• CPC Class Codes: B01J 31/223 At least two oxygen atoms present in one at least bidentate or bridging ligand
• CPC Class Codes: B01J 31/2243 At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• CPC Class Codes: B01J 31/2265 Carbenes or carbynes, i.e.(image)
• CPC Class Codes: B01J 31/2286 Alkynes, e.g. acetylides
• CPC Class Codes: C07F 11/00 Compounds containing elements of Groups 6 or 16 of the Periodic Table
• CPC Class Codes: C08F 32/04 having one carbon-to-carbon double bond
• CPC Class Codes: C08F 4/69 Chromium, molybdenum, tungsten or compounds thereof
• CPC Class Codes: C08F 4/69206 Tridentate ligand
• CPC Class Codes: C08F 4/78 selected from chromium, molybdenum or tungsten
• CPC Class Codes: C08G 2261/13 Morphological aspects
• CPC Class Codes: C08G 2261/3324 derived from norbornene
• CPC Class Codes: C08G 2261/418 Ring opening metathesis polymerisation [ROMP]
• CPC Class Codes: C08G 61/08 of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring

Abstract

A tetraanionic OCO pincer ligand metal-oxo-alkylidene complex is prepared from a trianionic pincer ligand supported metal-alkylidyne. The metal can be tungsten or other group 5-7 transition metal. The tetraanionic pincer ligand metal-oxo-alkylidene complex, a trianionic OCO pincer ligand metal complex, or a trianionic ONO pincer ligand metal complex can be used to polymerize cycloalkenes. The poly(cycloalkene)s are predominantly cis-alkene macrocyclics.

Claims

1. A tetraanionic pincer ligand metal-oxo-alkylidene complex of the structure:

2. The tetraanionic pincer ligand metal-oxo-alkylidene complex according to claim 1, wherein the structure is:

3. The tetraanionic pincer ligand metal-oxo-alkylidene complex according to claim 1, wherein the structure is:

4. The tetraanionic pincer ligand metal-oxo-alkylidene complex according to claim 1, wherein the structure is:

5. The tetraanionic pincer ligand metal-oxo-alkylidene complex according to claim 1, wherein the structure is:

6. A method to prepare a tetraanionic pincer ligand metal-oxo-alkylidene complex according to claim 1, comprising:

providing a trianionic pincer ligand supported metal-alkylidyne complex;

combining the trianionic pincer ligand supported metal-alkylidyne complex with carbon dioxide, carbon disulfide, or a mixture thereof; and

optionally, warming the mixture of trianionic pincer ligand metal-alkylidyne complex with carbon dioxide, wherein a tetraanionic pincer ligand metal-oxo-alkylidene complex is formed.