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Directed Gas Phase Formation of the Elusive Silylgermylidyne Radical (H 3 SiGe, X 2 A′′)
Author(s) -
Yang Zhenghai,
Doddipatla Srinivas,
Kaiser Ralf I.,
Krasnoukhov Vladislav S.,
Azyazov Valeriy N.,
Mebel Alexander M.
Publication year - 2021
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000913
Subject(s) - chemistry , isomerization , germanium , radical , germane , hydrogen , van der waals force , silicon , photochemistry , gas phase , hydrocarbon , hydrogen bond , computational chemistry , molecule , organic chemistry , catalysis
Abstract The previously unknown silylgermylidyne radical (H 3 SiGe; X 2 A′′) was prepared via the bimolecular gas phase reaction of ground state silylidyne radicals (SiH; X 2 Π) with germane (GeH 4 ; X 1 A 1 ) 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 (H 3 GeSiH 2 ). A hydrogen migration isomerizes this intermediate to the silylgermyl radical (H 2 GeSiH 3 ), which undergoes a hydrogen shift to an exotic, hydrogen‐bridged germylidynesilane intermediate (H 3 Si(μ‐H)GeH); this species emits molecular hydrogen forming the silylgermylidyne radical (H 3 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; C 2 H 5 ) eventually affording detailed insights into an exotic chemistry and intriguing chemical bonding of silicon‐germanium species at the microscopic level exploiting crossed molecular beams.