Invited
Catalytic metal-hydride regeneration from metal-alkoxides

Organoactinide complexes have been extensively studied in the last decade as catalysts for several organic transformations. Polymerization of alkenes, oligomerization, intermolecular hydroamination, hydrosilylation of terminal alkynes, and 1,1-insertion of isonitriles into terminal alkynes comprise some of these processes.

However, due to the high oxophilicity of the actinide complexes, all the substrates containing oxygen atoms were excluded, because of the expected low activity of these complexes due to the predictable oxygen-actinide interaction. In our attempts to discover new catalytic reactions for actinide-based complexes, we have found their surprising activity towards the polymerization of cyclic mono- and diesters.¹

To expand the scope of the actinides in catalysis, we have pursued the dimerization of aldehydes to esters.² These discoveries arouse the conceptual question about performing catalytic processes with substrates containing a nucleophilic motif by organoactinides. In addition, we have reported on the reactivity of mono(imidazolin-2-iminato) actinide (IV) complexes in the catalytic dimerization of aldehydes, displaying a high catalytic activity and selectivity toward the asymmetrically substituted ester.³

Here, we will present new organoactinide complexes that are excellent catalysts for the activation of heterocumulenes with amines, phosphines thiols, yielding the respective
insertion products. In addition, we will present the catalytic regeneration of Th-H with from the corresponding Th-alkoxide motifs via a hydroboration of aldehydes, ketone and in the
dearomatization of pyridines and other aromatic systems. ^4,5

^{1 Sharma, M.; Andrea, T.; Brookes, N. J.; Yates, B. F.; Eisen, M. S. J. Amer. Chem. Soc. 2011, 133, 1341.
2 Karmel, I.S.R.; Fridman, N.; Tamm, M.; Eisen, M.S. J. Am. Chem. Soc. 2014, 136, 17180.
3 Karmel, I. S. R.; Tamm, M.; Eisen, M. S. Angew. Chem. 2015, 54, 12422-12425.
4 (a) Liu, H.; Kulbitski, K.; Tamm, M.; Eisen. M. S. Chemistry – Eur. J. 2018, 24, 5738-5742.
(b) Liu, H.; Khononov, M.; M.; Eisen. M. S. ACS Catalysis 2018, 8, 3673-3677.
5 Ghatak, T.; Makarov, K.; Fridman, N.; Eisen, M. S. Chem. Commun., 2018, 54, 11001-11004}