Aerobic Co or Cu/NHPI-catalyzed oxidation of hydride siloxanes: Synthesis of siloxanols
A highly efficient preparative method for the synthesis of siloxanols based on aerobic Co(OAc)2 or Cu(OAc)2/NHPI-catalyzed oxidation of hydride siloxanes using "green", commercially available, simple inexpensive reagents and mild reaction conditions has been proposed. This is a general reaction for the synthesis of mono-, oligo- and polymeric siloxanols with various structures (linear, branched and cyclic).
Arzumanyan, Ashot V.,Goncharova, Irina K.,Novikov, Roman A.,Milenin, Sergey A.,Boldyrev, Konstantin L.,Solyev, Pavel N.,Tkachev, Yaroslav V.,Volodin, Alexander D.,Smol'Yakov, Alexander F.,Korlyukov, Alexander A.,Muzafarov, Aziz M.
COMPLEX COMPOUND, AND PRODUCTION METHOD OF SILOXANE
PROBLEM TO BE SOLVED: To provide a production method of siloxane capable of producing siloxane efficiently; and to provide a compound useful in production of siloxane. SOLUTION: In a method, siloxane is produced efficiently, by progressing a dehydrogenati
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Paragraph 0048; 0049
(2019/07/13)
Selective hydrosiloxane synthesis: Via dehydrogenative coupling of silanols with hydrosilanes catalysed by Fe complexes bearing a tetradentate PNNP ligand
A well-defined iron complex system was established using PNNP-R (R = Ph and Cy) as a strong σ-donating ligand with a rigid meridional tetradentate structure. Reactive Fe(0) complexes [{Fe(PNNP-R)}2(μ-N2)] were synthesized by a reaction of the corresponding iron dihalide with NaBEt3H and structurally characterized. The reaction proceeded via the iron dihydride intermediate [Fe(H)2(PNNP-R)], which underwent H2 reductive elimination, supporting the hemilabile behavior of PNNP-R. [{Fe(PNNP-R)}2(μ-N2)] catalyzed the dehydrogenative coupling of silanols with silanes to selectively form various hydrosiloxanes, which are important building blocks for the synthesis of a range of siloxane compounds. This system exhibited higher catalytic efficiency than the previously reported precious-metal-catalyzed systems.