Dehydrogenative coupling of alcohol with hydrosilane catalyzed by an iron complex

Photoactivated silicon–oxygen and silicon–nitrogen heterodehydrocoupling with a commercially available iron compound

“…44 Moreover, while literature on isolated piano-stool iron-alkoxides or -amides is scarce, Nakazawa and co-workers have implicated piano-stool ironalkoxide and iron-thio intermediates in catalytic Si-O and Si-S heterodehydrocoupling, respectively. 26,27 Scheme 2. Proposed mechanism for Si-O and Si-N heterodehydrocoupling catalysed by 1.…”

“…Although Si-O and Si-S heterodehydrocoupling by Nakazawa and co-workers via Cp(CO)2FeMe is a similar system, starting from 1 and the prevalence of 18-electron compounds such as 4, 5, and 6 as intermediates shows that a different activation step is likely here. 26,27 A 17-electron σ-silane intermediate could be a potential intermediate and highly reactive. 52 We have been unable to differentiate the influence of 17-electron compounds other than Cp(CO)2Fe • , and the presence 4 and 5 challenge such a pathway in the absence of better data.…”

“…25 Although Si-O heterodehydrocoupling using 1 has not been reported, derivatives of 1 catalyzing similar transformations are known, most notably by Nakazawa and co-workers in Si-O and Si-S heterodehydrocoupling via Cp(CO)2FeMe. 26,27 Herein, we report 1 as a heterodehydrocoupling catalyst in the formation of Si-O and Si-N bonds. Mechanistic study of the reaction indicates nucleophilic attack of a silane by an intermediate iron-alkoxide or -amide, but more germane to the further development of iron, complete activation of 1 was not achieved in these reactions, which suggests that full activation of iron catalyst precursors is an important pursuit in developing base metal catalysis.…”

Morphological and functional aspects of zeolite filled siloxane composite foams

“…Just after 5 min of curing, a relevant foaming was obtained [Figure (b)]. Then, in order to complete the dehydrogenative coupling reaction between siloxane compounds and zeolite filler, a postcuring stage (24 h at 60 °C) was carried out . Finally, when the foaming stage was concluded the porous structure could be demolded [Figure (c)] and the foamed composite structure was ready to be characterized [Figure (d)].…”

Catalytic Formation of Silicon–Heteroatom (N, P, O, S) Bonds

“…In 2015, the Nakazawa group presented an earth‐abundant metal catalyst of iron [CpFe(CO) 2 Me] (Cp=η 5 ‐cyclopentadienyl) to catalyze Si−O dehydrocoupling . The major drawback of this process is the elevated temperature (80 °C) and the use of a large excess amount of the hydrosilane.…”