A Cationic Zinc Hydride Cluster Stabilized by an N-Heterocyclic Carbene: Synthesis, Reactivity, and Hydrosilylation Catalysis

Arnab Rit (1) , Alessandro Zanardi (1) , Thomas Spaniol (1) , Laurent Maron (2) , Jun Okuda (1)

1 IAC RWTH - Institute of Inorganic Chemistry [Aachen]
2 LPCNO - Laboratoire de physique et chimie des nano-objets

The trinuclear cationic zinc hydride cluster [(IMes)3Zn3H4(THF)](BPh4)2 (1) was obtained either by protonation of the neutral zinc dihydride [(IMes)ZnH2]2 with a Brønsted acid or by addition of the putative zinc dication [(IMes)Zn(THF)]2+. A triply bridged thiophenolato complex 2 was formed upon oxidation of 1 with PhSSPh. Protonolysis of 1 by methanol or water gave the corresponding trinuclear dicationic derivatives. At ambient temperature, 1 catalyzed the hydrosilylation of aldehydes, ketones, and nitriles. Carbon dioxide was also hydrosilylated under forcing conditions when using (EtO)3SiH, giving silylformate as the main product.

Mots clés: Carbon dioxide; Homogeneous catalysis; Hydrides; N-heterocyclic carbenes; Zinc

Domaines: Chimie-Physique [physics.chem-ph]

Arnab Rit, Alessandro Zanardi, Thomas Spaniol, Laurent Maron, Jun Okuda. A Cationic Zinc Hydride Cluster Stabilized by an N-Heterocyclic Carbene: Synthesis, Reactivity, and Hydrosilylation Catalysis. Angewandte Chemie International Edition, 2014, 53 (48), pp.13273-13277. ⟨hal-01969490⟩