Directed Gas Phase Formation of the Elusive Silylgermylidyne Radical (H3SiGe, X2A′′). Issue 2 (16th December 2020)

• Record Type: Journal Article
• Authors: Yang, Zhenghai; Doddipatla, Srinivas; Kaiser, Ralf I.; Krasnoukhov, Vladislav S.; Azyazov, Valeriy N.; Mebel, Alexander M.
• Is Part Of: Chemphyschem. Volume 22:Issue 2(2021)
• Page Start: 184
• Page End: 191
• Publication Date: 2020-12-16
• Subjects: gas-phase reactions -- germane -- reaction dynamics -- silicon-germanium bond -- silylidyne; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.202000913
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: The previously unknown silylgermylidyne radical (H3 SiGe; X 2 A′′) was prepared via the bimolecular gas phase reaction of ground state silylidyne radicals (SiH; X 2 Π) with germane (GeH4 ; X 1 A1 ) under single collision conditions in crossed molecular beams experiments. This reaction begins with the formation of a van der Waals complex followed by insertion of silylidyne into a germanium‐hydrogen bond forming the germylsilyl radical (H3 GeSiH2 ). A hydrogen migration isomerizes this intermediate to the silylgermyl radical (H2 GeSiH3 ), which undergoes a hydrogen shift to an exotic, hydrogen‐bridged germylidynesilane intermediate (H3 Si(μ‐H)GeH); this species emits molecular hydrogen forming the silylgermylidyne radical (H3 SiGe). Our study offers a remarkable glance at the complex reaction dynamics and inherent isomerization processes of the silicon‐germanium system, which are quite distinct from those of the isovalent hydrocarbon system (ethyl radical; C2 H5 ) eventually affording detailed insights into an exotic chemistry and intriguing chemical bonding of silicon‐germanium species at the microscopic level exploiting crossed molecular beams. Abstract : Elusive radical : The previously unexplored silylgermylidyne radical (H3 SiGe) is synthesized in the gas phase through silicon‐germanium bond linkage of the silylidyne radical (SiH) with germane (GeH4 ) under single collision conditions.