Double and Triple Si-H-M Bridge Bonds: Matrix Infrared Spectra and Theoretical Calculations for Reaction Products of Silane with Ti, Zr, and Hf Atoms

Bing Xu; Peipei Shi; Tengfei Huang; Xuefeng Wang; Lester Andrews

doi:10.1021/acs.jpca.6b12217

Double and Triple Si-H-M Bridge Bonds: Matrix Infrared Spectra and Theoretical Calculations for Reaction Products of Silane with Ti, Zr, and Hf Atoms

J Phys Chem A. 2017 May 25;121(20):3898-3908. doi: 10.1021/acs.jpca.6b12217. Epub 2017 May 12.

Authors

Bing Xu¹, Peipei Shi¹, Tengfei Huang¹, Xuefeng Wang¹, Lester Andrews²

Affiliations

¹ School of Chemical Science and Engineering, Shanghai Key Lab of Chemical Assessment and Sustainability, Tongji University , Shanghai, 200092, China.
² Department of Chemistry, University of Virginia , Charlottesville, Virginia 22904 United States.

PMID: 28471677
DOI: 10.1021/acs.jpca.6b12217

Abstract

Infrared spectra of matrix isolated dibridged Si(μ-H)₂MH₂ and tribridged Si(μ-H)₃MH molecules (M = Zr and Hf) were observed following the laser-ablated metal atom reactions with SiH₄ during condensation in excess argon and neon, but only the latter species was observed with titanium. Assignments of the major vibrational modes, which included terminal MH, MH₂ and hydrogen bridge Si-H-M stretching modes, were confirmed by the appropriate SiD₄ isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). The Si-H-M hydrogen bridge bond is calculated as weak covalent interaction and compared with the C-H···M agostic interaction in terms of electron localization function (ELF) analysis and noncovalent interaction index (NCI) calculations. Furthermore, the different products of Ti, Zr, and Hf reactions with SiH₄ are discussed in detail.