Catalyst for ring expansion metathesis polymerization of cyclic monomers

Patent metadata

Field	Value
Publication number	US-10639620-B2
Application number	US-201615760730-A
Country	US
Kind code	B2
Filing date	Sep 19, 2016
Priority date	Sep 18, 2015
Publication date	May 5, 2020
Grant date	May 5, 2020

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.

First claim

We claim:

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

where: Z is independently O or S; R comprises, independently, H, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, or alkyl containing 5-22 carbon atoms; R′ is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, alkyl containing 5-22 carbon atoms, phenyl, naphthyl, or aryl containing 13-22 carbon atoms; X is O, N, S, P, or Se; R″, independently, is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, alkyl containing 5-22 carbon atoms, phenyl, naphthyl, aryl containing 13-22 carbon atoms, or two R″ are an alkylene containing 4-6 carbon atoms combined with a single X to form a heterocycle; n is 1 to 3; and M is a group 5-7 transition metal.

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.

Assignees

• Univ Florida

Inventors

• Veige Adam S
• Almeida Gonsales Stella

Classifications

• C08F4/69

  Chromium, molybdenum, tungsten or compounds thereof · CPC title

• B01J31/2286

  Alkynes, e.g. acetylides · CPC title

• B01J2540/10

  Non-coordinating groups comprising only oxygen beside carbon or hydrogen · CPC title

• B01J31/223 Primary

  At least two oxygen atoms present in one at least bidentate or bridging ligand · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title