Group 14 Hydrides with Low Valent Elements for Activation of Small Molecules (2011)

Transition metal compounds are well known as activators of small molecules, and they serve as efficient catalysts for a variety of homogeneous and heterogeneous transformations. In contrast, there is a general feeling that main group compounds cannot act as efficient catalysts because of their inability to activate small molecules. Traditionally, the activation of small molecules is considered one of the key steps during a catalytic cycle with transition metals. As a consequence, researchers have long neglected the full range of possibilities in harnessing main group elements for the design of efficient catalysts. Recent developments, however, have made it possible to synthesize main group compounds with low-valent elements capable of activating small molecules. In particular, the judicious use of sterically appropriate ligands has been successful in preparing and stabilizing a variety of Group 14 hydrides with low-valent elements. In this Account, we discuss recent advances in the synthesis of Group 14 hydrides with low-valent elements and assess their potential as small-molecule activators. Group 14, which comprises the nonmetal C, the semimetals Si and Ge, and the metals Sn and Pb, was for years a source of hydrides with the Group 14 element almost exclusively in tetravalent form. Synthetic difficulties and the low stability of Group 14 hydrides in lower oxidation states were difficult to overcome. But in 2000, a divalent Sn(II) hydride was prepared as a stable compound through the incorporation of sterically encumbered aromatic ligands. More recently, the stabilization of GeH(2) and SnH(2) complexes using an N-heterocyclic carbene (NHC) as a donor and BH(3) or a metal carbonyl complex as an acceptor was reported. A similar strategy was also employed to synthesize the Si(II) hydride. This class of hydrides may be considered coordinatively saturated, with the lone pair of electrons on the Group 14 elements taking part in coordination. We discuss the large-scale synthesis of hydrides of the form LMH (where M is Ge or Sn, L is CH(N(Ar)(CMe))(2), and Ar is 2,6-iPr(2)C(6)H(3)), which has made it possible to test their reactivity in the activation of small molecules. Unlike the tetravalent Group 14 hydrides, the Ge(II) and Sn(II) hydrides were found to be able to activate a number of small molecules in the absence of any externally added catalyst. For example, the Ge(II) hydride and Sn(II) hydride can activate CO(2), and the reaction results in the formation of Ge(II) and Sn(II) esters of formic acid. This product represents a prototype of a new class of compounds of Group 14 elements. Moreover, we examined the activation of carbonyl compounds, alkynes, diazo and azo compounds, azides, and compounds containing the C═N bond. These Group 14 hydrides with low-valent elements are shown to be able to activate a number of important small molecules with C≡C, C═O, N═N, and C═N bonds. The activation of small molecules is an important step forward in the realization of main group catalyst development. Although it is not yet customary to assay the potential of newly synthesized main group compounds for small-molecule activation, our results offer good reason to do so.