2002(A)Using Soluble Polymers To Recover Catalysts and Ligands

Using Soluble Polymers To Recover Catalysts and Ligands

David E.Bergbreiter*

Department of Chemistry,Texas A&M University,P.O.Box30012,College Station,Texas77842-3012

Received March5,2002

Contents

I.Introduction3346

II.Early Work3346

A.Linear Polystyrene-Bound Catalysts3346

B.Asymmetric Catalysis with Linear

Polymer-Supported Catalysts

3347

C.Water-Soluble Polymer Supports for Catalysts3347

1.Proteinaceous Supports3347

2.Polar Polymer Supports3348

D.Polymers Supporting Catalysts with Thermally

Reversible Solubility

3348

1.Sirotherm Resins3348

2.Poly(vinylpyridine)Supports3348

E.Biphasic Systems Employing Soluble

Polymer-Supported Catalysts

3348

F.Inorganic Polymer Supports3349

1.Polyphosphazene Supports3349

2.Silicon-Containing Polymers as Catalyst

Supports

3349

G.General Features Common to Early Work3350

III.Characterization Advantages of Soluble Polymer

Supports

3350

A.1H NMR Spectroscopy3350

B.13C NMR Spectroscopy3351

C.Relaxation Time Effects3352

D.UV−Vis,Fluorescence,and IR Spectroscopic

Studies of Soluble Polymer-Bound Ligands

and Catalysts

3353

IV.General Features of Soluble Polymer-Supported

Catalyst Activity

3354

V.Strategies for Separation and Recovery of

Soluble Polymer-Bound Ligands and Catalysts

3355

A.Solid/Liquid Separations of

Polyethylene-Bound Catalysts

3356

1.Rhodium(I)Hydrogenation Catalysts on

Polyethylene Supports

3357

2.Polyethylene-Bound Nickel(0)Diene

Cyclooligomerization Catalysts

3358

3.Polyethylene-Bound Palladium(0)

Catalysts

3359

4.Polyethylene-Bound Palladium(II)

Catalysts

3359

5.Polyethylene-Bound Hydroformylation

Catalysts

3360

6.Polyethylene-Bound Ruthenium Catalysts3360

7.Polyethylene-Bound Europium(III)

Complexes 3361

8.Polyethylene-Bound Rhodium(II)

Cyclopropanation Catalysts

3362

9.Polyethylene-Bound Chiral Rhodium(II)

Catalysts

3362

10.Polyethylene-Bound Phase-Transfer

Catalysts

3362

11.Polyethylene-Bound Tin Catalysts3363

12.Polyethylene-Bound Polymerization

Catalysts

3363

B.Solid/Liquid Separations of Catalysts on

Polymers with Inverse

Temperature-Dependent Solubility

3364

1.“Smart”Thermally Responsive Catalysts3365

2.Poly(N-isopropylacrylamide)-Bound

Catalysts

3365

C.Solid/Liquid Separations of Catalysts on Acid-

and Base-Soluble Polymers

3366

D.Solid/Liquid Separations of Catalysts after

Solvent Precipitation of Polymers

3367

1.Poly(alkene oxide)-Bound Catalysts3367

2.Polyacrylonitrile-Bound Scandium

Catalysts

3368

3.Chiral Rigid-Rod Polymers Containing

Binaphthyl Groups as Catalyst Supports

3368

4.Binaphthyl-Containing Dendritic

Polymer-Supported Catalysts in

Asymmetric Hydrogenation

3370

5.Linear Polystyrene-Bound Catalysts3370

6.Dendrimer-Supported Catalysts3370

7.Poly(dimethylsiloxane)-Supported

Catalysts

3371

8.Polyacrylate-Supported Catalysts3371

E.Liquid/Liquid Separation of Water-Soluble

Polymer-Bound Catalysts under Aqueous

Biphasic Conditions

3371

1.Water-Soluble Polymer-Bound

Hydrogenation Catalysts Derived from

Poly(acrylic acid)or Polyethylenimine

Used under Biphasic Conditions

3372

2.Water-Soluble Polymer-Bound

Hydroformylation Catalysts Derived from

Poly(acrylic acid)or Polyethylenimine

Used under Biphasic Conditions

3372

3.Water-Soluble Polymer-Bound Asymmetric

Hydrogenation Catalysts Used under

Biphasic Conditions

3373

4.Modified Polymers as Supports for

Hydroformylation Catalysis under Biphasic

Conditions

3373

5.Proteins as Supports for Hydroformylation

Catalysis under Biphasic Conditions

3374

*E-mail:bergbreiter@.

3345 Chem.Rev.2002,102,3345−3384

10.1021/cr010343v CCC:$39.75©2002American Chemical Society

Published on Web08/30/2002