Top Organomet Chem (2016) 59: 139–186
DOI: 10.1007/3418_2015_161
# Springer International Publishing Switzerland 2015
Published online: 21 November 2015
“Early–Late” Heterobimetallic Catalysis
and Beyond
Ewen Bodio, Michel Picquet, and Pierre Le Gendre
Abstract By combining an ever-increasing number of catalysts or catalytic functions, cooperative catalysis is a research area that grows fast. In the field, “early–late”
heterobimetallic complexes are rather old objects but they still continue to fascinate
chemists because of their latent reactivity. After a brief and concise overview of
cooperative catalysis, this review focuses on “early–late” heterobimetallic complexes
that were used in catalysis over the last decades. Examples of dual catalysis using
early and late metal partners are also described. This chapter ends with an opening
towards therapeutic applications of “early–late” heterobimetallic complexes.
Keywords Bifunctional catalysis • Bimetallic complexes • Cooperative catalysis •
Dual catalysis • “Early–late” heterobimetallic complexes
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
2 Cooperative Catalysis Besides “Early–Late” Heterobimetallic Catalysis . . . . . . . . . . . . . . . . 141
2.1 Bifunctional Organocatalysis, Frustrated Lewis Pairs (FLP), and Organo–Metal
Cooperative Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
2.2 Metal–Ligand Bifunctional Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
2.3 Homobimetallic Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
2.4 Dual Catalysis from “Neighbor” Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
2.5 Heterobimetallic Catalysis from “Neighbor” Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
3 “Early–Late” Heterobimetallic Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.1 Group 8/Group 4–5 Heterobimetallic Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.2 Group 9/Group 4–5 Heterobimetallic Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
3.3 Group 10/Group 4–5 Heterobimetallic Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
E. Bodio, M. Picquet, and P. Le Gendre (*)
Institut de Chimie Mole ´culaire de l’Universite ´ de Bourgogne (ICMUB, UMR CNRS 6302),
Univ. Bourgogne Franche-Comte ´, B^ at. Sciences de Mirande, Avenue Alain Savary, BP 47870,
21078 Dijon, Cedex, France
e-mail: pierre.le-gendre@u-bourgogne.fr
DOI: 10.1007/3418_2015_161
# Springer International Publishing Switzerland 2015
Published online: 21 November 2015
“Early–Late” Heterobimetallic Catalysis
and Beyond
Ewen Bodio, Michel Picquet, and Pierre Le Gendre
Abstract By combining an ever-increasing number of catalysts or catalytic functions, cooperative catalysis is a research area that grows fast. In the field, “early–late”
heterobimetallic complexes are rather old objects but they still continue to fascinate
chemists because of their latent reactivity. After a brief and concise overview of
cooperative catalysis, this review focuses on “early–late” heterobimetallic complexes
that were used in catalysis over the last decades. Examples of dual catalysis using
early and late metal partners are also described. This chapter ends with an opening
towards therapeutic applications of “early–late” heterobimetallic complexes.
Keywords Bifunctional catalysis • Bimetallic complexes • Cooperative catalysis •
Dual catalysis • “Early–late” heterobimetallic complexes
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
2 Cooperative Catalysis Besides “Early–Late” Heterobimetallic Catalysis . . . . . . . . . . . . . . . . 141
2.1 Bifunctional Organocatalysis, Frustrated Lewis Pairs (FLP), and Organo–Metal
Cooperative Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
2.2 Metal–Ligand Bifunctional Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
2.3 Homobimetallic Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
2.4 Dual Catalysis from “Neighbor” Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
2.5 Heterobimetallic Catalysis from “Neighbor” Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
3 “Early–Late” Heterobimetallic Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.1 Group 8/Group 4–5 Heterobimetallic Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.2 Group 9/Group 4–5 Heterobimetallic Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
3.3 Group 10/Group 4–5 Heterobimetallic Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
E. Bodio, M. Picquet, and P. Le Gendre (*)
Institut de Chimie Mole ´culaire de l’Universite ´ de Bourgogne (ICMUB, UMR CNRS 6302),
Univ. Bourgogne Franche-Comte ´, B^ at. Sciences de Mirande, Avenue Alain Savary, BP 47870,
21078 Dijon, Cedex, France
e-mail: pierre.le-gendre@u-bourgogne.fr