Studies of the thermal and photochemical decomposition mechanisms of But2Se in the presence or absence of Me2Zn using deuterium labelled analogues

Mass-spectrometric monitoring of the thermally induced decomposition of trimethylgallium, tris(tert-butyl)gallium, and triethylantimony at low pressure conditions

“…These paths are seen to be dominating in the present case, which indicates the high surface coverage. The recombinative desorption, which was reported for the thermolysis of GaMe 3 [14,35] and Se t Bu 2 [37], is observed here for the first time during the thermolysis of SbEt 3 . This reaction increasingly dominates with increased temperature and forms n-butane with an activation energy of 161 kJ/mol (A ϭ 10 13 s Ϫ1 ).…”

“…The production of i-butane in addition to i-butene was also observed during the thermolysis of Se t Bu 2 [37]. These authors assumed the occurrence of a homolytic cleavage of the Se-C [37] or Ga-C [30] bonds, producing t Bu radical that initiates a surface or gas-phase chain reaction. The trend exhibited by i-butane, Figure 3, indicates that the assumed homolytic cleavage reaction is favored in a narrow temperature range (300 -500°C).…”

Coinage Metal Complexes with Di‐tertiary‐butyl Sulfide as Precursors with Ultra‐Low Decomposition Temperature

“…The non‐silylated di‐tertiary‐butyl chalcogenides, t Bu 2 E (E=S, Se, Te) have been studied for their facile decomposition at low temperature, although their exact decomposition mechanism has been a subject of intense debate [40,41] . The possible initial steps in the decomposition include (i) C−E bond cleavage to give t Bu .…”

“…A residual mass of 51.8 % at 250 °C indicates the formation of gold as the end product (calculated value 52 %). As described before, the low decomposition temperature of 1 – 3 can be attributed to the availability of a facile decomposition path in the t Bu 2 S group [40] . To better understand the decomposition mechanism of this ligand, the gold complex 3 , which does not have any other organic group than the t Bu 2 S group, was further studied by the TGA‐mass spectrometry (TGA‐MS).…”

“…[39] The non-silylated di-tertiary-butyl chalcogenides, t Bu 2 E (E = S, Se, Te) have been studied for their facile decomposition at low temperature, although their exact decomposition mechanism has been a subject of intense debate. [40,41] The possible initial steps in the decomposition include (i) CÀ E bond cleavage to give t Bu * and t BuE * radicals, and (ii) β À H elimination to give isobutene and tertiary-butyl chalcogenol (Scheme 1). While it was proposed using deuterium labelled experiments that t Bu 2 Se undergoes decomposition via initial SeÀ C bond cleavage, [40] recently it was shown using ab initio calculations that the nonradical β-H elimination pathway could almost fully account for the decomposition of t Bu 2 S, even though radical reactions do have an effect on the product distribution.…”