Organometallic Chemistry and Hydroelementation

Organometallic Chemistry and Hydroelementation

GECOM-CONCOORD 2016
Organometallic Chemistry and Hydroelementation – Dehydrocoupling
Catalysis of Heavy Alkaline-Earth and Divalent Rare-Earth Elements
C. Bellini, Bo Liu, Sorin Rosca, Yann Sarazin, and Jean-François Carpentier
Organometallics, Materials and Catalysis laboratories, Institut des Sciences Chimiques de Rennes, UMR 6226
CNRS – University of Rennes 1, Rennes, 35042 Cedex, France; [email protected]
Means to stabilize complexes of the large, oxophilic alkaline-earth metals (Ae = Ca, Sr and Ba)
against ligand scrambling have become available. As a result, the interest in the reactivity of these
main group metals and their implementation in catalysis is rising sharply. We have shown that noncovalent interactions such as Ae...H–Si and Ae...F–C afford stable, yet highly reactive complexes which
catalyze polymerization hydroelementation and dehydrocoupling reactions.[1-3]
The preparation of families of heteroleptic alkyl and amide complexes will be presented here,
highlighting the importance of the ancillary ligand (aminophenolate, β-diketiminate and imino-anilide)
and Ae...H–Si agostic bonding in their stability.[2,3,4] The reactivity of these new Ae complexes is
examined in relation with several key organic transformations leading to C–P, C–N and Si–N bond
formation: ketone hydrophosphonylation,[5] intermolecular and hydroamination and hydrophosphination of activated alkenes,[3,6] cyclohydroamination of amino-alkenes,[4,6,7] and dehydrocoupling of
hydrosilanes and amines.[8-10] The catalytic activity in those processes almost systematically increases
with the metal size: Ca < Sr < Ba. Key structure-reactivity trends will be discussed in light of kinetic
and mechanistic investigations. Recent results obtained in the hydrophosphination of alkenes with
catalysts based on divalent lanthanides, which are closely related to Ae elements, will be discussed as
well.[11]
[1]
[2]
[3]
[4]
[5]
[6]
[7]
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N. Romero, S.-C. Roşca, Y. Sarazin, J.-F. Carpentier, L. Vendier, S. Mallet-Ladeira, C. Dinoi, M. Etienne,
Chem. Eur. J. 2015, 21, 4115.
[8] C. Bellini, J.-F. Carpentier, S. Tobisch, Y. Sarazin, Angew. Chem. Int. Ed. 2015, 54, 7679-7683.
[9] C. Bellini, V. Dorcet, J.-F. Carpentier, S. Tobisch, Y. Sarazin, Chem. Eur. J. 2016, 22, in press. DOI:
10.1002/chem.201504316.
[10] C. Bellini, C. Orione, Jean-François Carpentier, Y. Sarazin, Angew. Chem. Int. Ed. 2016, 55, in press. DOI:
10.1002/anie.201511342R1.
[11] I. V. Basalov, S. C. Roşca, D. M. Lyubov, A. N. Selikhov, G. K. Fukin, Y. Sarazin, J.-F. Carpentier, A. A.
Trifonov, Inorg. Chem. 2014, 53, 1654.