ATI Stabilized Germylene Cation as a Cyanosilylation Catalyst for Aldehydes and Ketones.

ABSTRACT

The aminotroponiminate (ATI) ligand stabilized germylene cation [(i-Bu)2ATIGe][B(C6F5)4] (2) is found to be an efficient low-valent main-group catalyst for the cyanosilylation of aldehydes and ketones (ATI=aminotroponiminate). It was synthesized by reacting [(i-Bu)2ATIGeCl] (1) with Na[B(C6F5)4]. The catalytic cyanosilylation of diverse aliphatic and aromatic carbonyl compounds (aldehydes and ketones) using 0.075-0.75 mol% of compound 2 was completed within 5-45 min. The catalytic efficiency seen with aliphatic aldehydes was around 15,800 h-1, making compound 2 a capable low-valent main-group catalyst for the aldehyde and ketone cyanosilylation reactions. Further, DFT calculations reveal a pronounced charge localization at the germanium atom of compound 2, leading to its superior catalytic performance.