Research
Creation of innovative catalysts and reactive species that enable efficient transformation of unreactive bonds and molecules has been a formidable challenge in synthetic chemistry and catalysis science. We have been studying on cooperation between two metals, two organoelements, and two reaction systems to realize unique catalysis and reactivity, which enable unprecedented molecular transformations. We have been working on design, synthesis, and utilization of heterobimetallic transition metal catalysts having metal-metal bonds supported by precisely designed organic scaffolds, which enable efficient transformation of carbon dioxide and other organic molecules. One of successful examples was demonstrated in hydrosilylation of carbon dioxide, where an Al–Pd bimetallic complex exhibited the highest catalytic activity ever reported.1,4,6,7,9 We also achieved an unprecedented C–C σ-bond cleavage reaction of umbiphilic phosphine-borane compounds under photoirradiation conditions enabled by transiently generated excited Frustrated Lewis Pairs.2,5,8 Furthermore, we have recently demonstrated that the new cooperative catalysis merging photochemistry and transition metal catalysis enables unprecedented C–C σ-bond cleavage and functionalization of arylketones.3
Selected references
- Tuning Photoredox Catalysis of Ruthenium with Palladium: Synthesis of Heterobimetallic Ru–Pd Complexes that Enable Efficient Photochemical Reduction of CO2
S. Yang, Y. Morita, Y. Nakamura, N. Iwasawa, J. Takaya
J. Am. Chem. Soc. 146, 12288 (2024). - Reversible Boron-insertion into Aromatic C–C Bonds
K. Kuroki, T. Ito, J. Takaya
Angew. Chem., Int. Ed., 62, e202312980 (2023). - Merging the Norrish Type I Reaction and Transition Metal Catalysis: Photo- and Rh-Promoted Borylation of C–C σ-Bonds of Aryl Ketones
Y. Fujimaki, N. Iwasawa, J. Takaya
Chem. Sci., 14, 1960 (2023). - Rhodium-Catalyzed Chemoselective Hydrosilylation of Nitriles to an Imine Oxidation Level Enabled by a Pincer-type Group 13 Metallylene Ligand
J. Takaya, K. Ogawa, R. Nakaya, N. Iwasawa
ACS Catal., 10, 12223 (2020). - Photo-Promoted Skeletal Rearrangement of Phosphine-Borane Frustrated Lewis Pairs Involving Cleavage of Unstrained C–C σ–Bonds
T. Ito, N. Iwasawa and J. Takaya
Angew. Chem., Int. Ed., 59, 11913 (2020). - Rhodium-Catalyzed C−H Activation Enabled by an Indium Metalloligand
R. Yamada, N. Iwasawa, J. Takaya
Angew. Chem., Int. Ed., 58, 17251 (2019). - Stabilized Gallylene in a Pincer Type Ligand: Synthesis, Structure, and Reactivity of PGaIP-Ir Complexes
N. Saito, J. Takaya, N. Iwasawa
Angew. Chem., Int. Ed., 58, 9998 (2019). - Ruthenium‐Catalyzed ortho C−H Borylation of Arylphosphines
K. Fukuda, N. Iwasawa, J. Takaya
Angew. Chem., Int. Ed. 58, 2850 (2019). - Synthesis, Structure, and Catalysis of Palladium Complexes Bearing a Group 13 Metalloligand: Remarkable Effect of an Aluminum-Metalloligand in Hydrosilylation of CO2
J. Takaya and N. Iwasawa
J. Am. Chem. Soc., 139, 6074 (2017).