Salt-Free Reduction of Transition Metal Complexes for Generating Catalytically Active Low-Valent Species

Abstract

Low-valent transition metal species have attracted special attention due to their important role in the activation of small molecules. Reduction of high-valent transition metal complexes is the general strategy for preparing highly reactive low-valent transition metal species without any π-acidic ligands, and strong reductants, such as amalgams of alkaline and alkaline-earth metals, zinc dust, and alkylmetal reagents, are conventionally used as the reductants. Generation of the low-valent metal species using the reductants, however, is always accompanied by reductant-derived metal wastes as well as overreduced impurities. Thus, such the reducing method sometimes not only hampers isolation of the desired low-valent metal complexes but also delays their reactivity or catalytic performance due to coordination of the reductant-derived metal salt to the reactive metal center.

References

Arteaga-Muller, R. A.; Tsurugi, H.; Saito, T.; Yanagawa, M.; Oda, S.; Mashima, K. J. Am. Chem. Soc. 2009, 131, 5370.

Tsurugi, H.; Saito, T.; Tanahashi, H.; Arnold, J.; Mashima, K. J. Am. Chem. Soc. 2011, 133, 18673.

Tsurugi, H.; Tanahashi, H.; Nishiyama, H.; Fegler, W.; Saito, T.; Sauer, A.; Okuda, J.; Mashima, K. J. Am. Chem. Soc. 2013, 135, 5986.

Saito, T.; Nishiyama, H.; Tanahashi, H.; Kawakita, K.; Tsurugi, H.; Mashima, K. J. Am.

Hayato Tsurugi

Hayato Tsurugi is an associate professor of the Graduate School of Engineering Science, Osaka University. He received his Ph.D. degree in 2006 from Osaka University under the supervision of Prof. K. Mashima. From 2006 to 2008, he worked with Prof. M. Miura as an assistant professor at the Graduate School of Engineering, Osaka University.

In 2008, he joined Prof. K. Mashima's group at the Graduate School of Engineering Science, Osaka University as an assistant professor, and then promoted to an associate professor in 2010. His research interests are in the areas of organometallic chemistry, including catalytic applications for direct C-H transformation, radical coupling reactions, α-olefin oligomerization/polymerization, as well as coordination chemistry with transition metals for synthesizing homo/heterometal clusters, and the development of new reduction methods using main-group element compounds.