Stable carbenes and related species as powerful tools in organic, organometallic, and inorganic chemistry

It will be shown that the peculiar electronic and steric properties of cyclic (alkyl)(amino)carbenes (CAACs) (1,2) and other stable singlet carbenes allow for the stabilization of unusual diamagnetic and paramagnetic main group element species. As examples, we will describe the preparation of room temperature stable boron, antimony-, and even carbon-centered neutral and cationic radicals.

We will also show that CAACs allow for the isolation of catalytically active complexes, which were supposed to be only transient intermediates. Among them, bis(copper) complexes  involved in the very popular CuAAC reaction (Click Chemistry) will be discussed (3). We will show that this discovery allows for the development of novel catalytic transformations (4).

Another part of the lecture will be devoted to the synthesis, reactivity and coordination behavior of the first stable phosphinidene  (5,6,7).

References:

1.   M. Soleilhavoup, G. Bertrand, Acc. Chem. Res. 2015, 48, 256-266.

2. M. Melaimi, R. Jazzar, M. Soleilhavoup, G. Bertrand, Angew. Chem. Int. Ed. 2017, 56, DOI: 10.1002/anie.201702148

3.  L. Jin, D. R. Tolentino, M. Melaimi, G. Bertrand, Sci. Adv. 2015, 1, e1500304.

4.  E. A. Romero, J. L. Peltier, R. Jazzar, G. Bertrand, Chem. Sci. 2017, 8, 165-168.

5.  L. Liu, D. A. Ruiz, D. Munz, G. Bertrand, Chem 2016, 1, 27-29.

6.  M. M. Hansmann,, R. Jazzar, G. Bertrand, J. Am. Chem. Soc. 2016, 138, 8356-8359.

7.  M. M. Hansmann, G. Bertrand, J. Am. Chem. Soc. 2016, 138, 15885-15888.