Promotion of TH3 (T = Si and Ge) group transfer within a tetrel bond by a cation-π interaction

Na Liu; Qiaozhuo Wu; Qingzhong Li; Steve Scheiner

doi:10.1039/d1cp05323j

Promotion of TH₃ (T = Si and Ge) group transfer within a tetrel bond by a cation-π interaction

Phys Chem Chem Phys. 2022 Jan 4;24(2):1113-1119. doi: 10.1039/d1cp05323j.

Authors

Na Liu¹, Qiaozhuo Wu¹, Qingzhong Li¹, Steve Scheiner²

Affiliations

¹ The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China. [email protected].
² Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322-0300, USA. [email protected].

PMID: 34927648
DOI: 10.1039/d1cp05323j

Abstract

The possibility of the transfer of the TH₃ group across a tetrel bond is considered by ab initio calculations. The TB is constructed by pairing PhTH₃ (Ph = phenyl; T = Si and Ge) with bases NH₃, NHCH₂, and the C₃N₂H₄ carbene. The TH₃ moves toward the base but only by a small amount in these dimers. However, when a Be²⁺ or Mg²⁺ dication is placed above the phenyl ring, the tetrel bond strength is greatly magnified reaching up to nearly 100 kcal mol^-1. This dication also induces a much higher degree of transfer which can be best categorized as half-transfer for the two N-bases and a near complete transfer for the carbene.