Top Organomet Chem (2021) 69: 303–324
https://doi.org/10.1007/3418_2020_52
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 7 August 2020
Iridium-Catalyzed Homogeneous
Hydrogenation and Hydrosilylation
of Carbon Dioxide
Francisco J. Fernández-Alvarez and Luis A. Oro
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
2 Recent Advances on Iridium-Catalyzed CO 2 Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
2.1 Iridium-Catalyzed Formic Acid or Formate Preparation from CO 2 and H 2 . . . . . . . . . 305
2.2 Iridium-Catalyzed Methanol Preparation from Direct Hydrogenation of CO 2 . . . . . . 309
2.3 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
3 Recent Advances on Iridium-Catalyzed CO 2 Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
3.1 Iridium-Catalyzed CO 2 Hydrosilylation to Silylformate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
3.2 Iridium-Catalyzed Reduction of CO 2 to Methoxysilanes with Silicon-Hydrides . . . 315
3.3 Iridium-Catalyzed Reduction of CO 2 to Methane with Silicon-Hydrides . . . . . . . . . . . 317
4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
Abstract The knowledge of the potential of transition metal-based complexes as
catalysts for the reduction of CO 2 has grown significantly over the last few decades.
This chapter focuses on the progress made during recent years in the field of
homogeneous iridium-catalyzed reduction of CO 2 by using hydrogen and/or silicon
hydrides as reducing agents, comparing them with homogeneous catalysts based on
other transition metals.
The reported studies on iridium-catalyzed CO 2 reduction processes show that an
important point to keep in mind when designing a catalyst is the nature of the
reducing agent (hydrogen, hydrosilanes, and/or hydrosiloxanes). Thus, iridium(III)
The original version of this chapter was revised. A correction to this chapter can be found at
https://doi.org/10.1007/3418_2020_73
F. J. Fernández-Alvarez (*) and L. A. Oro (*)
Departamento de Química Inorgánica, Facultad de Ciencias, Instituto de Síntesis Química y
Catálisis Homogénea (ISQCH), Universidad de Zaragoza – CSIC, Zaragoza, Spain
e-mail: paco@unizar.es; oro@unizar.es
https://doi.org/10.1007/3418_2020_52
# The Author(s), under exclusive license to Springer Nature Switzerland AG 2020,
corrected publication 2020
Published online: 7 August 2020
Iridium-Catalyzed Homogeneous
Hydrogenation and Hydrosilylation
of Carbon Dioxide
Francisco J. Fernández-Alvarez and Luis A. Oro
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
2 Recent Advances on Iridium-Catalyzed CO 2 Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
2.1 Iridium-Catalyzed Formic Acid or Formate Preparation from CO 2 and H 2 . . . . . . . . . 305
2.2 Iridium-Catalyzed Methanol Preparation from Direct Hydrogenation of CO 2 . . . . . . 309
2.3 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
3 Recent Advances on Iridium-Catalyzed CO 2 Hydrosilylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
3.1 Iridium-Catalyzed CO 2 Hydrosilylation to Silylformate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
3.2 Iridium-Catalyzed Reduction of CO 2 to Methoxysilanes with Silicon-Hydrides . . . 315
3.3 Iridium-Catalyzed Reduction of CO 2 to Methane with Silicon-Hydrides . . . . . . . . . . . 317
4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
Abstract The knowledge of the potential of transition metal-based complexes as
catalysts for the reduction of CO 2 has grown significantly over the last few decades.
This chapter focuses on the progress made during recent years in the field of
homogeneous iridium-catalyzed reduction of CO 2 by using hydrogen and/or silicon
hydrides as reducing agents, comparing them with homogeneous catalysts based on
other transition metals.
The reported studies on iridium-catalyzed CO 2 reduction processes show that an
important point to keep in mind when designing a catalyst is the nature of the
reducing agent (hydrogen, hydrosilanes, and/or hydrosiloxanes). Thus, iridium(III)
The original version of this chapter was revised. A correction to this chapter can be found at
https://doi.org/10.1007/3418_2020_73
F. J. Fernández-Alvarez (*) and L. A. Oro (*)
Departamento de Química Inorgánica, Facultad de Ciencias, Instituto de Síntesis Química y
Catálisis Homogénea (ISQCH), Universidad de Zaragoza – CSIC, Zaragoza, Spain
e-mail: paco@unizar.es; oro@unizar.es